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# Characterization of halogen-bridged binuclear metal complexes as hybridized two-band materials

## I Introduction

The family of transition-metal (M) linear-chain complexes containing bridging halogens (X) has a long history of research  especially in the chemical field. The conventional class  of these materials, which we refer to as MX chains, is represented by the Wolffram red salts ($`\text{M}=\text{Pt},\text{X}=\text{Cl}`$) and has been fascinating both chemists and physicists due to its novel properties, such as intense and dichroic charge-transfer absorption, strong resonance enhancement of Raman spectra, and luminescence with large Stokes shift, which all originate in the mixed-valence ground state. On the other hand, the synthesis of NiX compounds  which exhibit mono-valence magnetic ground states aroused a renewed interest in this system. Substituting the metals, bridging halogens, ligand molecules, and counter anions surrounding the one-dimensional chains, the tunability of the ground-state electronic structure was fully revealed . A pressure-induced reverse Peierls instability  was also demonstrated. All these observations can be understood as the competition between the Peierls and Mott insulators . Intrinsic multiband effects, together with competing electron-electron and electron-phonon interactions, raise a possibility of further ground states appearing, such as incommensurate (long-period) charge density waves , spin-Peierls states , and density waves on the halogen sublattice . A leading group  in Los Alamos National Laboratory presented an extensive two-band-model study covering the ground-state properties, excitation spectra, and quantum lattice fluctuations. The research trend is now shifting toward mixed-metal complexes , where the ground-state degeneracy is lifted and therefore the relaxation process of photogenerated excitons via solitons or polarons can efficiently be controlled.

In an attempt to explore further into this unique system, the new class of these materials, which we refer to as MMX chains, has been synthesized, where binuclear metal units are bridged by halogen ions. Thus-far synthesized MMX-chain compounds are classified into two groups: M2(dta)4I ($`\text{M}=\text{Pt},\text{Ni}`$; $`\text{dta}=\text{dithioacetate}=\text{CH}_3\text{CS}_2^{}`$)  and R4\[Pt2(pop)4X\]$``$$`n`$H2O ($`\text{X}=\text{Cl},\text{Br},\text{I}`$; $`\text{R}=\text{K},\text{NH}_4,\text{etc.}`$; $`\text{pop}=\text{diphosphonate}=\text{H}_2\text{P}_2\text{O}_5^{\mathrm{\hspace{0.17em}2}}`$) , which we hereafter refer to as “dta” and “pop” complexes. The binucleation of the metal sites does much more than simply increases the internal degrees of freedom of the electronic configuration:

(i) The formal oxidation state of metal ions is $`2.5+`$, that is mixed valency of M2+ and M3+, in MMX chains, whereas it is $`3+`$, that is, mixed valency of M2+ and M4+, in MX chains. There exists an unpaired electron per one metal-dimer unit of trapped valence M2+-M3+, while none at all in the corresponding unit of trapped valence M2+-M4+.

(ii) The direct M-M overlap contributes to the reduction of the effective on-site Coulomb repulsion and thus electrons can be more itinerant in MMX chains.

(iii) In the MX-chain system, metals are tightly locked together due to the hydrogen bonds between the amino-groups of the ligands and the counter anions. Therefore any dimerization of the metal sublattice has not yet been observed. In the MMX-chain system, adjacent metals are locked to each other by the surrounding ligands, but the metal-dimer moiety itself is rather movable especially in the dta complexes with neutral chain structures. Although there still exist weak van der Waals contacts between ligands against the Peierls instability in the dta complexes, Pt2(dta)4I has recently been reported to exhibit a dimerization of the metal sublattice .

(iv) Owing to the neutral chain structure, the band filling of the dta complexes might be varied.

Thus, the new class of the halogen-bridged metal complexes is highly potential in every aspect. Further efforts to synthesize general polynuclear metal complexes  stimulate our interest all the more.

The physical properties of the MMX-chain system are not so well established as the accumulated chemical knowledge. There is a hot argument about the valence structures of MMX chains. So far four types of the oxidation states have been pointed out, which are illustrated in Fig. 1. All but (a) are accompanied by lattice distortion, where the X sites are displaced maintaining the translational symmetry in (b), the M2 sublattice is dimerized in (c), and the X sublattice is dimerized in (d). In this notation, (a) represents spin-density-wave states of any kind as well as the paramagnetic (metallic) state.

The ground-state valence structure of the Cl- and Br-bridged Pt complexes of the pop family was extensively investigated by resonance Raman spectroscopy , X-ray single-crystal structure analyses , solid-state 31P nuclear-magnetic-resonance measurements , and polarized optical spectra , and was concluded to be (d). However, due to the small Peierls gap, the ground states of these materials can be tuned with pressure from the strongly valence-trapped state (d) toward the valence-delocalized state (a) (or possibly (c)) , where the pressure mainly contributes to the increase of the electron transfer between neighboring Pt2 moieties. Such charge fluctuations become more remarkable when bridging halogens are replaced by I . The valence transition is sensitive to the radius of the counter cations and the number of the water molecules as well.

For the dta complexes, on the other hand, the electronic structures seem to be more complicated and less established. X-ray photoelectron spectra of the Ni complexes  suggest the valence delocalization on the regular chain structure (a), which is convincing on the analogy of NiX chains with magnetic ground states characterized as Mott-Hubbard insulators . Although early measurements  on the Pt complexes of the dta series implied their structural similarities with the Ni complexes and the valence delocalization at room temperature, recent experiments  have reported another scenario for the valence structure of the Pt complexes: With decreasing temperature, there occurs a metal-semiconductor transition, that is, a transition from the averaged-valence state (a) to the trapped-valence state (b), at $`300`$ K, and further transition to the charge-ordering mode (c) follows around $`80`$ K. The valence structure (c) accompanied by the metal-sublattice dimerization is all the more interesting in relation to spin-Peierls fluctuations, which have never yet been observed in the MX-chain system.

In response to such stimulative observations, we here calculate the electronic structure of MMX compounds employing a $`\frac{5}{6}`$-filled two-band model. Under the notation of Fig. 1, the filled X $`p_z`$ orbitals are put out of account. It is sometimes assumed in phenomenological arguments and experimental investigations that unless the system is photoexcited and/or activated by hole doping, the halogen ions contribute no effective electron to the low-energy physics. The goal of this paper is to give a criterion for when the $`\frac{3}{4}`$-filled signle-band approximation is valid or invalid. We calculate ground-state phase diagrams within the Hartree-Fock approximation, where we analytically classify and characterize possible density-wave solutions making full use of symmetry properties. Based on the thus-revealed ground-state properties, we further carry out quantum Monte Carlo calculations of the thermal properties. Extensive analytical and numerical calculations bring us a wide view of the $`d`$-$`p`$-hybridized two-band electron-phonon system.

## II Hartree-Fock calculation based on a symmetry argument

### A Model Hamiltonian and Its Symmetry Properties

We introduce the $`\frac{5}{6}`$-filled one-dimensional two-band three-orbital extended Peierls-Hubbard Hamiltonian:

$``$ $`=`$ $`{\displaystyle \frac{K}{2}}{\displaystyle \underset{n}{}}\left(l_{1:n}^2+l_{2:n}^2\right)+{\displaystyle \underset{n,s}{}}\left[\left(\epsilon _\mathrm{M}\beta l_{1:n}\right)n_{1:n,s}+\left(\epsilon _\mathrm{M}+\beta l_{2:n}\right)n_{2:n,s}+\epsilon _\mathrm{X}n_{3:n,s}\right]`$ (1)
$``$ $`{\displaystyle \underset{n,s}{}}[(t_{\mathrm{MX}}\alpha l_{1:n})a_{1:n,s}^{}a_{3:n,s}+(t_{\mathrm{MX}}+\alpha l_{2:n})a_{2:n,s}^{}a_{3:n,s}+t_{\mathrm{MM}}a_{1:n,s}^{}a_{2:n1,s}+\mathrm{H}.\mathrm{c}.]`$ (2)
$`+`$ $`{\displaystyle \underset{n}{}}\left(U_\mathrm{M}n_{1:n,+}n_{1:n,}+U_\mathrm{M}n_{2:n,+}n_{2:n,}+U_\mathrm{X}n_{3:n,+}n_{3:n,}\right)`$ (3)
$`+`$ $`{\displaystyle \underset{n,s,s^{}}{}}\left(V_{\mathrm{MX}}n_{1:n,s}n_{3:n,s^{}}+V_{\mathrm{MX}}n_{2:n,s}n_{3:n,s^{}}+V_{\mathrm{MM}}n_{1:n,s}n_{2:n1,s^{}}\right),`$ (4)
where $`n_{i:n,s}=a_{i:n,s}^{}a_{i:n,s}`$ with $`a_{i:n,s}^{}`$ being the creation operator of an electron with spin $`s=\pm `$ (up and down) for the M $`d_{z^2}`$ ($`i=1,2`$) or X $`p_z`$ ($`i=3`$) orbital in the $`n`$th MXM unit, and $`l_{i:n}=u_{3:n}u_{i:n}`$ with $`u_{i:n}`$ being the chain-direction displacement of the metal ($`i=1,2`$) or halogen ($`i=3`$) in the $`n`$th MXM unit from its equilibrium position. $`\alpha `$ and $`\beta `$ are, respectively, the intersite and intrasite el-ph coupling constants, while $`K`$ is the metal-halogen spring constant. We assume, based on the thus-far reported experimental observations, that every M2 moiety is not deformed, namely, $`u_{1:n}=u_{2:n1}`$. $`\epsilon _\mathrm{M}`$ and $`\epsilon _\mathrm{X}`$ are the on-site energies (electron affinities) of isolated metal and halogen atoms, respectively. Since $`\epsilon _\mathrm{M}`$ is usually larger than $`\epsilon _\mathrm{X}`$, we neglect the weak alternation of the halogen-ion on-site energies. The electron hoppings between these levels are modeled by $`t_{\mathrm{MM}}`$ and $`t_{\mathrm{MX}}`$, whereas the electron-electron Coulomb interactions by $`U_\mathrm{M}`$, $`U_\mathrm{X}`$, $`V_{\mathrm{MM}}`$, and $`V_{\mathrm{MX}}`$. Coulomb interactions between neighboring metal and halogen ions may in principle alternate in accordance with lattice displacements in a two-band description. However, $`V_{\mathrm{MX}}`$ itself is rather small due to the ligands surrounding metals and its alternate component $`\delta V_{\mathrm{MX}}`$ is further reduced by the factor $`l_{i:n}/r`$ with $`r`$ being the M-X distance in the undistorted lattice. Therefore, any alternation of Coulomb interactions is usually neglected. We take $`N`$ for the number of unit cells in the following. Let us rewrite the Hamiltonian compactly in the momentum space as

$``$ $`=`$ $`{\displaystyle \underset{i,j}{}}{\displaystyle \underset{k,q}{}}{\displaystyle \underset{s,s^{}}{}}i:k+q,s|t|j:k,s^{}a_{i:k+q,s}^{}a_{j:k,s^{}}`$ (5)
$`+`$ $`{\displaystyle \frac{1}{2}}{\displaystyle \underset{i,j,m,n}{}}{\displaystyle \underset{k,k^{},q}{}}{\displaystyle \underset{s,s^{},t,t^{}}{}}i:k+q,s;m:k^{},t|v|j:k,s^{};n:k^{}+q,t^{}a_{i:k+q,s}^{}a_{m:k^{},t}^{}a_{n:k^{}+q,t^{}}a_{j:k,s^{}}`$ (6)
$`+`$ $`{\displaystyle \frac{K}{2}}{\displaystyle \underset{q}{}}[u_{1:q}u_{1:q}^{}+u_{2:q}u_{2:q}^{}+2u_{3:q}u_{3:q}^{}(\mathrm{e}^{\mathrm{i}q/3}u_{1:q}u_{3:q}^{}+\mathrm{e}^{\mathrm{i}q/3}u_{2:q}u_{3:q}^{}+\mathrm{c}.\mathrm{c}.)],`$ (7)
where we have set the unit-cell length (the distance between neighboring halogen ions) equal to unity. The momentum representation of the interactions can straightforwardly be obtained from the Fourier transform of the original Hamiltonian (4) and we learn

$`i:k+q,s|t|j:k,s^{}=i:k+q|t|j:k\delta _{ss^{}},`$ (8)
$`i:k+q,s;m:k^{},t|v|j:k,s^{};n:k^{}+q,t^{}`$ (9)
$`=i:k+q;m:k^{}|v|j:k;n:k^{}+q\delta _{ss^{}}\delta _{tt^{}}.`$ (10)
The most essential process of the Hartree-Fock approximation must be the introduction of order parameters. A symmetry argument  allows us to systematically derive density-wave solutions and reduce the following numerical efforts to the minimum necessary. As far as we consider the normal states, that is, unless the gauge symmetry is broken, the symmetry group of the present system is given by

$$𝐆=𝐏\times 𝐒\times 𝐓,$$
(11)
where $`𝐏=𝐋𝐂_2`$ is the space group of a linear chain with the one-dimensional translation group $`𝐋`$ whose basis vector is the unit-cell translation $`l`$, $`𝐒`$ is the group of spin-rotation, and $`𝐓`$ is the group of time reversal. Group actions on the electron operators are defined in Table I, where $`l𝐋`$, $`C_2𝐂_2`$, $`u(𝒆,\theta )=\sigma ^0\mathrm{cos}(\theta /2)(𝝈𝒆)\mathrm{sin}(\theta /2)𝐒`$, and $`t𝐓`$ with $`\sigma ^0`$ and $`𝝈=(\sigma ^x,\sigma ^y,\sigma ^z)`$ being the $`2\times 2`$ unit matrix and a vector composed of the Pauli-matrices, respectively.

Let $`\stackrel{ˇ}{G}`$ denote the irreducible representations of G over the real number field, where their representation space is spanned by the Hermitian operators {$`a_{i:k,s}^{}a_{j:k^{},s^{}}`$}. There is a one-to-one correspondence between $`\stackrel{ˇ}{G}`$ and broken-symmetry phases of density-wave type . Any representation $`\stackrel{ˇ}{G}`$ is obtained as a Kronecker product of the irreducible real representations of $`𝐏`$, $`𝐒`$, and $`𝐓`$:

$$\stackrel{ˇ}{G}=\stackrel{ˇ}{P}\stackrel{ˇ}{S}\stackrel{ˇ}{T}.$$
(12)
$`\stackrel{ˇ}{P}`$ is characterized by an ordering vector $`q`$ in the Brillouin zone and an irreducible representation of its little group $`𝐏(q)`$, and is therefore labeled $`q\stackrel{ˇ}{P}(q)`$. The relevant representations of $`𝐒`$ are given by

$$\begin{array}{cc}\stackrel{ˇ}{S}^0(u(𝒆,\theta ))=1\hfill & \text{(nonmagnetic)},\hfill \\ \stackrel{ˇ}{S}^1(u(𝒆,\theta ))=O(u(𝒆,\theta ))\hfill & \text{(magnetic)},\hfill \end{array}$$
(13)
where $`O(u(𝒆,\theta ))`$ is the $`3\times 3`$ orthogonal matrix satisfying $`u(𝒆,\theta )𝝈^\lambda u^{}(𝒆,\theta )=_{\mu =x,y,z}[O(u(𝒆,\theta ))]_{\lambda \mu }𝝈^\mu (\lambda =x,y,z)`$, whereas those of $`𝐓`$ by

$$\begin{array}{cc}\stackrel{ˇ}{T}^0(t)=1\hfill & \text{(symmetric)},\hfill \\ \stackrel{ˇ}{T}^1(t)=1\hfill & \text{(antisymmetric)}.\hfill \end{array}$$
(14)
The representations $`\stackrel{ˇ}{P}\stackrel{ˇ}{S}^0\stackrel{ˇ}{T}^0`$, $`\stackrel{ˇ}{P}\stackrel{ˇ}{S}^1\stackrel{ˇ}{T}^1`$, $`\stackrel{ˇ}{P}\stackrel{ˇ}{S}^0\stackrel{ˇ}{T}^1`$, and $`\stackrel{ˇ}{P}\stackrel{ˇ}{S}^1\stackrel{ˇ}{T}^0`$ correspond to charge-density-wave (CDW), spin-density-wave (SDW), charge-current-wave (CCW), and spin-current-wave (SCW) states, respectively. Here in one dimension, the current-wave states either result in the one-way uniform flow or break the charge-conservation law, and are therefore less interesting. We consider density waves of $`q=0`$ and $`q=\pi `$, which are labeled $`\mathrm{\Gamma }`$ and $`X`$, respectively. Since $`𝐏(\mathrm{\Gamma })=𝐏(X)=𝐂_2`$, $`\stackrel{ˇ}{P}(\mathrm{\Gamma })`$ and $`\stackrel{ˇ}{P}(X)`$ are either $`A`$ ($`C_2`$-symmetric) or $`B`$ ($`C_2`$-antisymmetric) representation of $`𝐂_2`$.

### B Broken-symmetry solutions

Now the mean-field Hamiltonian is given by

$`_{\mathrm{HF}}`$ $`=`$ $`{\displaystyle \underset{i,j}{}}{\displaystyle \underset{k,s,s^{}}{}}{\displaystyle \underset{\lambda }{}}[x_{ij}^\lambda (\mathrm{\Gamma };k)a_{i:k,s}^{}a_{j:k,s^{}}`$ (16)
$`+x_{ij}^\lambda (X;k)a_{i:k+\pi ,s}^{}a_{j:k,s^{}}]\sigma _{ss^{}}^\lambda .`$
Here the self-consistent fields $`x_{ij}^\lambda (\mathrm{\Gamma };k)`$ and $`x_{ij}^\lambda (X;k)`$ are described as

$`x_{ij}^0(\mathrm{\Gamma };k)=i:k|t|j:k+{\displaystyle \underset{m,n}{}}{\displaystyle \underset{k^{}}{}}\rho _{nm}^0(\mathrm{\Gamma };k^{})`$ (17)
$`\times (2i:k;m:k^{}|v|j:k;n:k^{}`$ (18)
$`i:k;m:k^{}|v|n:k^{};j:k),`$ (19)
$`x_{ij}^0(X;k)=i:k+\pi |t|j:k+{\displaystyle \underset{m,n}{}}{\displaystyle \underset{k^{}}{}}\rho _{nm}^0(X;k^{}+\pi )`$ (20)
$`\times (2i:k+\pi ;m:k^{}|v|j:k;n:k^{}+\pi `$ (21)
$`i:k+\pi ;m:k^{}|v|n:k^{}+\pi ;j:k),`$ (22)
$`x_{ij}^z(\mathrm{\Gamma };k)={\displaystyle \underset{m,n}{}}{\displaystyle \underset{k^{}}{}}\rho _{nm}^z(\mathrm{\Gamma };k^{})`$ (23)
$`\times i:k;m:k^{}|v|n:k^{};j:k,`$ (24)
$`x_{ij}^z(X;k)={\displaystyle \underset{m,n}{}}{\displaystyle \underset{k^{}}{}}\rho _{nm}^z(X;k^{}+\pi )`$ (25)
$`\times i:k+\pi ;m:k^{}|v|n:k^{}+\pi ;j:k,`$ (26)
in terms of the density matrices

$`\rho _{ij}^\lambda (\mathrm{\Gamma };k)={\displaystyle \frac{1}{2}}{\displaystyle \underset{s,s^{}}{}}a_{j:k,s}^{}a_{i:k,s^{}}_{\mathrm{HF}}\sigma _{ss^{}}^\lambda ,`$ (27)
$`\rho _{ij}^\lambda (X;k)={\displaystyle \frac{1}{2}}{\displaystyle \underset{s,s^{}}{}}a_{j:k+\pi ,s}^{}a_{i:k,s^{}}_{\mathrm{HF}}\sigma _{ss^{}}^\lambda ,`$ (28)
where $`\mathrm{}_{\mathrm{HF}}`$ denotes the quantum average in a Hartree-Fock eigenstate. We note that no helical SDW solution ($`\lambda =x,y`$) is obtained from the present Hamiltonian. We decompose the Hamiltonian (16) as

$$_{\mathrm{HF}}=\underset{D=A,B}{}\underset{K=\mathrm{\Gamma },X}{}\underset{\lambda =0,z}{}h_{KD}^\lambda .$$
(29)
Here the irreducible component $`h_{KD}^\lambda `$ can be obtained through a general formula

$$h_{KD}^\lambda =\frac{d^{(D)}}{g}\underset{p𝐂_2}{}\chi ^{(D)}(p)px_{ij}^\lambda (K;k)a_{i:k,s}^{}a_{j:k,s^{}}\sigma _{ss^{}}^\lambda ,$$
(30)
where $`\chi ^{(D)}(p)`$ is the irreducible character of the $`D`$ representation for the group element $`p`$, $`g(=2)`$ is the order of $`𝐂_2`$, and $`d^{(D)}(=1)`$ is the dimension of $`D`$. Thus we obtain the broken-symmetry Hamiltonian for the representation $`KD\stackrel{ˇ}{S}^i\stackrel{ˇ}{T}^i`$ as $`_{\mathrm{HF}}(K;D)=h_{\mathrm{\Gamma }A}^0+h_{KD}^\lambda `$, where $`\lambda =0`$ ($`i=0`$) or $`\lambda =z`$ ($`i=1`$). We explicitly show $`h_{KD}^\lambda `$ in Appendix A.

In order to characterize each phase, we define local order parameters. The charge and spin densities on site $`i`$ at the $`n`$th MXM unit are, respectively, given by

$`d_{i:n}`$ $`=`$ $`{\displaystyle \underset{s}{}}a_{i:n,s}^{}a_{i:n,s}_{\mathrm{HF}},`$ (31)
$`s_{i:n}^z`$ $`=`$ $`{\displaystyle \frac{1}{2}}{\displaystyle \underset{s,s^{}}{}}a_{i:n,s}^{}a_{i:n,s^{}}_{\mathrm{HF}}\sigma _{ss^{}}^z,`$ (32)
while the bond and spin bond orders between site $`i`$ at the $`n`$th MXM unit and site $`j`$ at the $`m`$th MXM unit are, respectively, defined as

$`p_{i:n;j:m}`$ $`=`$ $`{\displaystyle \underset{s}{}}a_{i:n,s}^{}a_{j:m,s}_{\mathrm{HF}},`$ (33)
$`t_{i:n;j:m}^z`$ $`=`$ $`{\displaystyle \frac{1}{2}}{\displaystyle \underset{s,s^{}}{}}a_{i:n,s}^{}a_{j:n,s^{}}_{\mathrm{HF}}\sigma _{ss^{}}^z.`$ (34)
Though $`p_{i:n;j:m}`$ and $`t_{i:n;j:m}^z`$ can generally be complex, their imaginary parts are necessarily zero in our argument. The order parameters can also be described in terms of the density matrices (27) and (28). Demanding that the density matrices should have the same symmetry properties as their host Hamiltonian, we can qualitatively characterize all the density-wave solutions. We briefly describe their properties in the following and explicitly show the analytic consequences of the symmetry argument in Appendix B.

(a) $`\mathrm{\Gamma }A\stackrel{ˇ}{S}^0\stackrel{ˇ}{T}^0`$: The paramagnetic state with the full symmetry G, abbreviated as PM.

(b) $`\mathrm{\Gamma }B\stackrel{ˇ}{S}^0\stackrel{ˇ}{T}^0`$: Bond order wave with polarized charge densities on the M2 moieties, abbreviated as BOW.

(c) $`XA\stackrel{ˇ}{S}^0\stackrel{ˇ}{T}^0`$: Charge density wave on the X sublattice with alternate polarized charge densities on the M2 moieties, abbreviated as X-CDW.

(d) $`XB\stackrel{ˇ}{S}^0\stackrel{ˇ}{T}^0`$: Charge density wave on the M sublattice, abbreviated as M-CDW.

(e) $`\mathrm{\Gamma }A\stackrel{ˇ}{S}^1\stackrel{ˇ}{T}^1`$: Ferromagnetism on both M2 and X sublattices, abbreviated as FM.

(f) $`\mathrm{\Gamma }B\stackrel{ˇ}{S}^1\stackrel{ˇ}{T}^1`$: Spin bond order wave with polarized spin densities on the M2 moieties, abbreviated as SBOW.

(g) $`XA\stackrel{ˇ}{S}^1\stackrel{ˇ}{T}^1`$: Spin density wave on the X sublattice with alternate polarized spin densities on the M2 moieties, abbreviated as X-SDW.

(h) $`XB\stackrel{ˇ}{S}^1\stackrel{ˇ}{T}^1`$: Spin density wave on the M sublattice, abbreviated as M-SDW.

Here, $`\overline{\rho }_{ij}^\lambda (K;k)`$ and $`\stackrel{~}{\rho }_{ij}^\lambda (K;k)`$ denote the real and imaginary parts of $`\rho _{ij}^\lambda (K;k)`$, respectively. All the phases are schematically shown in Fig. 2. The nonmagnetic broken-symmetry phases (a)-(d), respectively, correspond to the oxidation states (a)-(d) in Fig. 1 in this order.

So far little interest has been taken in the electronic state of the halogen ions in the full belief that in comparison with the M $`d_{z^2}`$ orbitals, the X $`p_z`$ orbitals are stably filled and less effective, at least, in the ground state. Such an idea may relatively be valid for MX chains, but it is not the case any more for MMX chains where the metal sublattice can be distorted. Our symmetry argument suggests that the X-CDW (alternate charge-polarization) state should be characterized by the charge density wave on the X sublattice rather than any modulation on the M2 sublattice. If we add up the charge and spin densities on the adjacent metal sites in every M2 moiety, they indeed modulate in M-CDW and M-SDW, whereas they are uniform in X-CDW and X-SDW. Alternate charge densities on the X sublattice necessarily mean the oxidation of the halogen ions.

We learn much more from the symmetry argument. Magnetic instabilities are generally not coupled with phonons. Specifying vanishing and nonvanishing density matrices and obtaining the symmetry-definite Hartree-Fock energy expression, we find which type of electronic correlation is effective in stabilizing each density-wave state. The halogen on-site Coulomb repulsion $`U_\mathrm{X}`$ stabilizes X-SDW and destabilizes X-CDW, respectively, while it is much less relevant to the M-type density-wave states. Though the intradimer different-site Coulomb repulsion $`V_{\mathrm{MM}}`$ has little effect on the X-type density-wave states, it efficiently stabilizes both M-CDW and M-SDW states. This is somewhat surprising because the repulsive interaction $`V_{\mathrm{MM}}`$ favors charge disproportionation in the M2 moiety at the naivest consideration. The $`V_{\mathrm{MM}}`$ stabilization of the M-type density-wave states comes from the Hamiltonian component related to the field $`b_{XB}^\lambda `$ (see Eqs. (A18), (A46), and (A62)). We find that $`V_{\mathrm{MM}}`$ favorably contributes to the modulation of the intradimer electron transfer. The following numerical calculations show that the situation $`V_{\mathrm{MM}}>V_{\mathrm{MX}}`$ generally stabilizes the M-type density-wave states, whereas those of the X-type are relatively stabilized under $`V_{\mathrm{MM}}<V_{\mathrm{MX}}`$, provided any other factor, such as the alternation of transfer integrals, is put out of account.

### C Ground-state phase diagrams

Let us observe competing ground states numerically. We calculate the Hartree-Fock energies $`_{\mathrm{HF}}`$ at a sufficiently low temperature ($`k_\mathrm{B}T/t_{\mathrm{MX}}=0.025`$) in the thermodynamic limit ($`N\mathrm{}`$). We show in Fig. 3 typical ground-state phase diagrams at $`\frac{5}{6}`$ band filling, where the strength of any interaction is indicated setting both $`t_{\mathrm{MX}}`$ and $`K`$ equal to unity. In spite of plenty of parameters, the phase diagrams bring us a general view of the ground-state properties:

(i) Fundamentally, on-site Coulomb repulsions are advantageous to SDW states, whereas intersite repulsions to CDW states. This can be easily understood on the analogy of the $`U`$-$`V`$ competition between CDW and SDW states in the single-band extended Hubbard model. With increasing $`U`$, the antiferromagnetic spin alignments are replaced by FM.

(ii) The site-diagonal electron-phonon coupling $`\beta `$ is favorable for M-CDW, while the intersite coupling $`\alpha `$ for X-CDW. This is also convincing when we simplify the argument employing a single-band model. Without the X $`p_z`$ orbitals, the dimerization of the X sublattice is simply modeled by modulating on-site electron affinities, while that of the M2 sublattice results in the modulation of intersite hopping integrals just as polyacetylene . Thus, it is likely in the pop complexes that the interchain locking of the M2 sublattices due to counter ions effectively realizes the parametrization $`\beta >\alpha `$. $`\alpha `$-versus-$`\beta `$ phase diagrams have recently been calculated within a single-band approximation by Kuwabara and Yonemitsu , where the competition from this point of view can be observed in more detail. They report that $`\beta `$ and $`\alpha `$ favor M-CDW and X-CDW, respectively, but X-CDW is much more widely stabilized to the ground state than M-CDW, which is consistent with the present observations.

(iii) As far as the Coulomb interactions are concerned, $`U_\mathrm{M}`$ and $`V_{\mathrm{MM}}`$ contribute to the M-type density waves appearing, while $`U_\mathrm{X}`$ and $`V_{\mathrm{MX}}`$ to those of the X-type. If we neglect the intersite Coulomb repulsions and any modulation of transfer integrals, the phase diagram is rather understandable: For small $`U`$, M-CDW ($`\alpha <\beta `$) or X-CDW ($`\alpha \beta `$); for large $`U`$, FM; otherwise, M-SDW ($`U_\mathrm{M}U_\mathrm{X}\mathrm{\Delta }\epsilon `$) or X-SDW ($`U_\mathrm{M}U_\mathrm{X}\mathrm{\Delta }\epsilon `$). $`\mathrm{\Delta }\epsilon \epsilon _\mathrm{M}\epsilon _\mathrm{X}`$ may be recognized as the orbital-energy correction to the M-X competition .

(iv) The competition between M-CDW and X-CDW is sensitive to the modulation of transfer integrals as well. Provided $`\alpha `$ is not so large as $`\beta `$, M-CDW is stabilized under $`t_{\mathrm{MM}}>t_{\mathrm{MX}}`$, whereas it is replaced by X-CDW under $`t_{\mathrm{MM}}t_{\mathrm{MX}}`$. The orbital hybridization within every M2 moiety is essential in the valence-trapped M-CDW state, while it is the overlap of the $`d_\sigma ^{}`$ orbitals on neighboring M2 moieties that stabilizes the valence-delocalized X-CDW state. Based on semiempirical quantum-chemical band calculations, Borshch et al.  pointed out a possibility of the X-CDW-type valence structure being stabilized in this context. They revealed, restricting their argument to the Pt2(dta)4I compound, that twisting of the dta ligand reduces the electronic communication by $`\pi `$ delocalization between adjacent metal sites and ends in charge disproportionation within the M2 moiety. On the other hand, employing a single-band model, Baeriswyl and Bishop  pioneeringly suggested that with increasing M-X-M interdimer transfer integral, the distortion of the halogen sublattice should shrink and in the end the metal sublattice may begin to dimerize. Though their argument was mainly devoted to the MX-chain system, it is valid enough for the MMX-chain system as well. Such a behavior was indeed observed  applying pressure to a MMX material K4\[Pt2(pop)4Br\]$``$3H2O, which may be understood as a pressure-induced reverse Peierls instability.

At $`\frac{5}{6}`$ band filling, due to the perfect nesting of the Fermi surface with respect to $`q=\pi `$ phonons, $`X(q=\pi )`$-phases are predominantly stabilized. Therefore, doping of the system generally contributes to the stabilization of $`\mathrm{\Gamma }(q=0)`$-phases, though any doping of MMX chains has not yet been reported. At $`\frac{4}{6}`$ band filling, for example, an interesting competition between BOW and SBOW  is observed, that is, the competition between site-centered CDW and SDW states is replaced by that between bond-centered CDW and SDW states.

Now we are convinced that a single-band description of the M-type density waves (M-CDW and M-SDW) may be justified well, whereas the halogen $`p_z`$ orbitals should explicitly be taken into consideration in describing those of the X-type (X-CDW and X-SDW). In the next section, we further support this criterion using a quantum Monte Carlo technique. The pop and dta families will fully be characterized as approximate $`d_{z^2}`$-single-band materials and really $`d`$-$`p`$-hybridized two-band materials, respectively.

## III Quantum Monte Carlo approach

### A Numerical procedure

We employ a quantum Monte Carlo method  based on the checkerboard-type decomposition  of the partition function. We simulate the Hamiltonian (4), namely, we here make an adiabatic description of the phonon field. Starting with an arbitrary electron and lattice configuration, we update the electron configuration under the frozen phonon field and then update the lattice configuration under the fixed electron configuration by the heat-bath algorithm. At each Monte Carlo step, under the constraint $`u_{1:n}=u_{2:n1}`$, every site moves right or left by a sufficiently small unit $`\mathrm{\Delta }_{\mathrm{unit}}`$ or otherwise stays at the present position: $`\stackrel{~}{u}_{i:n}\stackrel{~}{u}_{i:n}+\delta \stackrel{~}{u}_{i:n}`$; $`\delta \stackrel{~}{u}_{i:n}=\mathrm{\Delta }_{\mathrm{unit}},\mathrm{\Delta }_{\mathrm{unit}},0`$, where $`\stackrel{~}{u}_{i:n}=\alpha u_{i:n}/t_{\mathrm{MX}}`$. $`\mathrm{\Delta }_{\mathrm{unit}}`$ is set equal to $`0.02`$. According to such movements of lattice sites, the bond configuration is updated as

$`\{\begin{array}{ccc}l_{1:n}\hfill & \hfill & l_{1:n}\delta u_{1:n}\hfill \\ l_{2:n1}\hfill & \hfill & l_{2:n1}\delta u_{1:n}\hfill \end{array}\mathrm{for}u_{1:n}u_{1:n}+\delta u_{1:n},`$ (37)
$`\{\begin{array}{ccc}l_{1:n}\hfill & \hfill & l_{1:n}+\delta u_{3:n}\hfill \\ l_{2:n}\hfill & \hfill & l_{2:n}+\delta u_{3:n}\hfill \end{array}\mathrm{for}u_{3:n}u_{3:n}+\delta u_{3:n},`$ (40)
where the total length of the lattice is kept unchanged.

Since it is difficult to handle negative weights with the world-line Monte Carlo algorithm , we further modify the original model (4) taking the metal-halogen hopping matrix elements to be

$`1:n|t|3:n=\{\begin{array}{c}t_{\mathrm{MX}}\alpha l_{1:n}\hfill \\ \mathrm{for}\stackrel{~}{u}_{3:n}\stackrel{~}{u}_{1:n}<1,\hfill \\ 0\mathrm{for}\stackrel{~}{u}_{3:n}\stackrel{~}{u}_{1:n}1,\hfill \end{array}`$ (44)
$`2:n|t|3:n=\{\begin{array}{c}t_{\mathrm{MX}}+\alpha l_{2:n}\hfill \\ \mathrm{for}\stackrel{~}{u}_{2:n}\stackrel{~}{u}_{3:n}<1,\hfill \\ 0\mathrm{for}\stackrel{~}{u}_{2:n}\stackrel{~}{u}_{3:n}1.\hfill \end{array}`$ (48)
As the atoms move away from each other, the overlap matrix elements go to zero and do not change sign. Therefore, the above modification makes sense from a physical point of view and may be justified with not-so-large coupling constants.

### B Magnetic susceptibility

We show in Fig. 5 temperature dependences of the magnetic susceptibility $`\chi `$ peculiar to M-CDW, X-CDW, M-SDW, and X-SDW. At every temperature, we have taken several Monte Carlo estimates changing the Trotter number $`n_\mathrm{T}`$ and their $`n_\mathrm{T}`$ dependence has been extrapolated to the $`n_\mathrm{T}\mathrm{}`$ limit. With decreasing temperature, the susceptibility shows a gentle upward slope and then exponentially vanishes in the CDW region, whereas in the SDW region it exhibits a significant enhancement, which is reminiscent of the low-temperature diverging behavior in Ni complexes . The two CDW-proper susceptibilities show differences as well as similarities. The much more rapid low-temperature decrease in the X-CDW state is likely to denote spin-Peierls like fluctuations. It is convincing that the susceptibility in the electronic-correlation-dominant region should also be saturated and turn decreasing at temperatures which are low enough to develop antiferromagnetic interactions between induced spin moments. However, the Monte Carlo estimates of the SDW-proper behavior at low temperatures are less convergent, where the numerical uncertainty is more than the symbol size. We should fundamentally take special care how we understand the present SDW-proper susceptibilities, because no antiferromagnetic spin-density long-range order is stabilized purely in one dimension. If we calculate beyond the mean-field approximation, any SDW gap is not obtained but SDW-like fluctuations grow more and more with decreasing temperature in the relevant region. However, the slightest interchain coupling stabilizes such fluctuations into a long-range order. The SDW states  widely observed in Ni complexes are thus stabilized, where hydrogen bonds and/or van der Waals contacts supply weak but essential interchain interactions. Therefore, concerning the SDW states as well, the present calculations remain suggestive. We learn that induced local spin moments are larger in the M-SDW state than in the X-SDW state.

In order to clarify the contribution from the X $`p_z`$ orbitals, we carry out further calculations of the susceptibility separating magnetizations on the M2 and X sublattices. We define the modified magnetic susceptibility $`\chi ^{(n_{\mathrm{orb}})}`$ as

$$\chi ^{(n_{\mathrm{orb}})}=\frac{g^2\mu _\mathrm{B}^2}{k_\mathrm{B}T}\left[(M^{(n_{\mathrm{orb}})})^2_{\mathrm{th}}M^{(n_{\mathrm{orb}})}_{\mathrm{th}}^2\right],$$
(49)
where $`\mathrm{}_{\mathrm{th}}`$ denotes the thermal average at a given temperature and

$$M^{(n_{\mathrm{orb}})}=\underset{n=1}{\overset{N}{}}\underset{i=1}{\overset{n_{\mathrm{orb}}}{}}\underset{s=\pm }{}\frac{s}{2}n_{i:n,s}.$$
(50)
The susceptibility coming from the M $`d_{z^2}`$ orbitals, $`\chi ^{\mathrm{MM}}`$, is given by $`\chi ^{(2)}`$, while $`\chi ^{(3)}`$ is the total susceptibility $`\chi ^{\mathrm{MMX}}`$, which has just shown in Fig. 5. We compare $`\chi ^{\mathrm{MM}}`$ with $`\chi ^{\mathrm{MMX}}`$ in Fig. 5. We find a clear contrast between $`\chi ^{\mathrm{MMX}}`$ and $`\chi ^{\mathrm{MM}}`$ in the parameter region stabilizing X-CDW to the ground state. Spin moments almost come from the M2 sublattice at high temperatures, where the system is expected to lie in the averaged-valence state, while $`\chi ^{\mathrm{MM}}`$ more and more deviates from $`\chi ^{\mathrm{MMX}}`$ and exhibits a diverging behavior with decreasing temperature. Thus, the X-CDW state is never stabilized without the $`p`$-electrons compensating the spin moments on the M2 sublattice. The M-CDW state also exhibits such an aspect but it is much less remarkable. There exists a similar contrast between M-SDW and X-SDW as well. The halo-

gen ions contribute no effective electron to the susceptibility in the M-SDW state, whereas all the electrons

are effective in the X-SDW state. We stress again that the contribution from the X sublattice, $`\chi ^{\mathrm{MMX}}\chi ^{\mathrm{MM}}`$, is not small in the X-SDW state, noting the different scales in Figs. 5(a) and 5(b).

### C Direct observation of the electronic states

Any path-integral method has the advantage of directly visualizing electronic states. We show in Figs. 6-9 Monte Carlo snapshots taken under the same parametri-

zations as the susceptibility calculations. Figures 6 and 7 clearly reveal the roles played by the $`d`$ and $`p`$ orbitals in the CDW states. The characteristic charge orders grow with decreasing temperature. In the ground state of the M-CDW type, the X $`p_z`$ orbitals are almost completely filled, whereas oxidized halogen ions appear in every other unit in the X-CDW-type ground state. It is obvious that the alternate charge densities on the X sublattice, rather than the alternation of polarized charge densities on the M2 sublattice, characterize the X-CDW state. Figures 8 and 9 also give a useful piece of information about the SDW states. The symmetry argument has concluded as follows: The antiferromagnetic spin ordering on the X sublattice characterizes X-SDW, where the M $`d_{z^2}`$ orbitals also contribute spin moments favoring a parallel alignment within each MXM unit (Fig. 2(g)); The antiferromagnetic spin ordering on the M2 sublattice characterizes M-SDW, where the spin moments favor a parallel alignment within each M2 moiety (Fig. 2(h)). Figures 8 and 9 convincingly display all these properties. We stress in particular that the X $`p_z`$ orbitals are all filled in Fig. 8(c), as well as in Fig. 6(c), which well shows the single-band character of the M-type density-wave states. Here we should be reminded that the present observations come from purely one-dimensional finite-chain calculations where any true antiferromagnetic long-range order can neither be stabilized nor be verified. The spin configuration indeed deviates from the perfect order peculiar to X-SDW here and there in Fig. 9(c). We find that domain walls prevent the characteristic local spin alignments from growing into the long-range order. Figure 8(c) just happens to contain no domain wall but longer-chain calculations still show the breakdown of the long-range order. It is, however, likely that M-SDW possesses more pronounced low-dimensional character than X-SDW.

It is also helpful in characterizing the SDW states to observe spin-spin correlations. We show in Fig. 10 spin correlation functions of a few types which are defined as

$`f^\mathrm{X}(r)={\displaystyle \underset{s,s^{}=\pm }{}}{\displaystyle \frac{ss^{}}{4}}n_{3:n,s}n_{3:n+r,s^{}}_{\mathrm{GS}},`$ (51)
$`f^{\mathrm{MM}}(r)={\displaystyle \underset{i,j=1}{\overset{2}{}}}{\displaystyle \underset{s,s^{}=\pm }{}}{\displaystyle \frac{ss^{}}{4}}n_{i:n,s}n_{j:n+r,s^{}}_{\mathrm{GS}},`$ (52)
$`f^{\mathrm{MXM}}(r)={\displaystyle \underset{i,j=1}{\overset{3}{}}}{\displaystyle \underset{s,s^{}=\pm }{}}{\displaystyle \frac{ss^{}}{4}}n_{i:n,s}n_{j:n+r,s^{}}_{\mathrm{GS}},`$ (53)
where $`\mathrm{}_{\mathrm{GS}}`$ denotes the canonical average at absolute zero point and may approximately be identified with the Monte Carlo sampling without any global flip along the Trotter direction in the zero-magnetization subspace at a sufficiently low temperature . In Fig. 10(a), no spin moment is essentially observed on the X sublattice, whereas there clearly exist antiferromagnetic spin-spin correlations on the M2 sublattice. In Fig. 10(b), we find weak but surviving antiferromagnetic spin-spin correlations on the X sublattice. In the X-SDW state, the spin moments induced on the X sites are not so large as those on the M2 moieties in the M-SDW state and their one-dimensional stabilization is less pronounced. However, observing $`f^{\mathrm{MXM}}(r)`$ as well, we may fully be convinced of the symmetry properties illustrated in Fig. 2(g) and the two-band character of X-SDW.

Finally in this section, let us turn back to Figs. 6-9 and take a look at finite-temperature snapshots. The spin correlations do not survive thermal fluctuations at all within one dimension, while the charge correlations are rather tough against increasing temperature. Such an aspect is more clearly demonstrated by M-CDW than by X-CDW. On the other hand, we have learned in Fig. 3 that X-CDW much more stably exists in the ground-state phase diagram. There may be a viewpoint that M-CDW is tough against thermal fluctuations but is sensitive to electronic correlations, while X-CDW is tough against quantum fluctuations but less survives thermal fluctuations. The M-CDW-type ground state is widely observed for the pop series of MMX chains , whereas the X-CDW-type one is found for the dta complexes . In (NH4)4\[Pt2(pop)4X\], the valence structure of the M-CDW type remains stable, in spite of minor formation of paramagnetic sites, up to room temperature . On the other hand, Pt2(dta)4I has been reported to undergoes a phase transition from X-CDW to BOW around 80 K, far prior to the metallic behavior above 300 K . These observations are qualitatively consistent with the present calculations. More extensive finite-temperature calculations will be reported elsewhere.

## IV Summary and Discussion

We have investigated the electronic properties of MMX chains both analytically and numerically with particular emphasis on the $`d`$-$`p`$-hybridization effect on competing charge- or spin-ordered states. Density-wave states of the M-type, M-CDW and M-SDW, may be described by a single-band model, whereas $`p`$-electrons play an essential role in stabilizing those of the X-type, X-CDW and X-SDW. Such views of these density-wave states are further supported by their band dispersions shown in Fig. 11. In comparison with M-CDW, X-CDW exhibits much more widespread energy bands due to an essential hybridization between the $`d`$ and $`p`$ orbitals. Based on the present calculations together with the thus-far reported experimental observations, we characterize the pop and dta families of MMX compounds as $`d_{z^2}`$-single-band and $`d`$-$`p`$-hybridized two-band materials, respectively. Besides this viewpoint, M-CDW and X-CDW present a few contrasts between them: They are, respectively, stable and instable against thermal fluctuations, while fragile and tough in the ground-state phase diagram.

At the naivest consideration, single-band descriptions of MMX chains may more or less be justified unless $`\mathrm{\Delta }\epsilon `$ is small enough. However, this is not necessarily the case under the existence of electronic correlations. If we employ a single-band Hamiltonian

$``$ $`=`$ $`{\displaystyle \frac{K}{2}}{\displaystyle \underset{n}{}}\left(l_{1:n}^2+l_{2:n}^2\right)\beta {\displaystyle \underset{n,s}{}}\left(l_{1:n}n_{1:n,s}l_{2:n}n_{2:n,s}\right)`$ (54)
$``$ $`{\displaystyle \underset{n,s}{}}[t_{\mathrm{MXM}}\alpha (l_{1:n}l_{2:n})](a_{1:n,s}^{}a_{2:n,s}+\mathrm{H}.\mathrm{c}.)`$ (55)
$``$ $`t_{\mathrm{MM}}{\displaystyle \underset{n,s}{}}(a_{1:n,s}^{}a_{2:n1,s}+\mathrm{H}.\mathrm{c}.)`$ (56)
$`+`$ $`U_\mathrm{M}{\displaystyle \underset{n}{}}\left(n_{1:n,+}n_{1:n,}+n_{2:n,+}n_{2:n,}\right)`$ (57)
$`+`$ $`{\displaystyle \underset{n,s,s^{}}{}}V_{\mathrm{MM}}n_{1:n,s}n_{2:n1,s^{}},`$ (58)
the resultant phase diagrams are qualitatively consistent with the present calculations without any Coulomb interaction. Once we turn on $`U_\mathrm{X}`$ in the two-band Hamiltonian (4), the single-band model (58), no matter how well all the parameters are renormalized, considerably underestimates the stability of the M2-sublattice-dimerized state in comparison with the present calculations. This fact is quite suggestive considering that $`U_\mathrm{X}`$ plays in favor of the oxidation of X- ions. Though assignment of any parameter is not yet successfully done in MMX compounds, $`U_\mathrm{M}`$ and $`U_\mathrm{X}`$ must be larger than the transfer energy and be of the order of eV on the analogy of MX compounds . Thus an explicit treatment of the X $`p_z`$ orbitals is indispensable to the dta complexes.

Experimental study on halogen-bridged multinuclear metal complexes is still in its early stage. X-ray photoelectron spectroscopy measurements on Pt2(dta)4I  are now under controversy. Polymorphism inherent in the pop-family compounds, partly originating from the contained water molecules, sometimes prevent us from observing the proper behavior of these materials. We hope the present research will stimulate further measurements and lead to close collaboration between theoretical and experimental investigations.

###### Acknowledgements.

The author is grateful to A. R. Bishop, K. Yonemitsu, and M. Kuwabara for useful discussions. He is thankful to H. Okamoto, H. Kitagawa, and K. Kanoda as well for helpful comments on MMX materials and measurements on them. This work was supported by the Japanese Ministry of Education, Science, and Culture and by the Sanyo-Broadcasting Foundation for Science and Culture. The numerical calculation was done using the facility of the Supercomputer Center, Institute for Solid State Physics, University of Tokyo.

## A Irreducible Hamiltonians

$`h_{\mathrm{\Gamma }A}^\lambda `$ $`=`$ $`a_{\mathrm{\Gamma }A}^\lambda {\displaystyle \underset{k,s,s^{}}{}}\left(a_{1:k,s}^{}a_{1:k,s^{}}+a_{2:k,s}^{}a_{2:k,s^{}}\right)\sigma _{ss^{}}^\lambda `$ (A1)
$`+`$ $`b_{\mathrm{\Gamma }A}^\lambda {\displaystyle \underset{k,s,s^{}}{}}a_{3:k,s}^{}a_{3:k,s^{}}\sigma _{ss^{}}^\lambda `$ (A2)
$`+`$ $`c_{\mathrm{\Gamma }A}^\lambda {\displaystyle \underset{k,s,s^{}}{}}[\mathrm{e}^{\mathrm{i}k/3}a_{1:k,s}^{}a_{2:k,s^{}}\sigma _{ss^{}}^\lambda +\mathrm{H}.\mathrm{c}.]`$ (A3)
$`+`$ $`d_{\mathrm{\Gamma }A}^\lambda {\displaystyle \underset{k,s,s^{}}{}}[(\mathrm{e}^{\mathrm{i}k/3}a_{1:k,s}^{}a_{3:k,s^{}}`$ (A5)
$`+\mathrm{e}^{\mathrm{i}k/3}a_{2:k,s}^{}a_{3:k,s^{}})\sigma _{ss^{}}^\lambda +\mathrm{H}.\mathrm{c}.],`$
$`h_{\mathrm{\Gamma }B}^\lambda `$ $`=`$ $`a_{\mathrm{\Gamma }B}^\lambda {\displaystyle \underset{k,s,s^{}}{}}\left(a_{1:k,s}^{}a_{1:k,s^{}}a_{2:k,s}^{}a_{2:k,s^{}}\right)\sigma _{ss^{}}^\lambda `$ (A6)
$`+`$ $`b_{\mathrm{\Gamma }B}^\lambda {\displaystyle \underset{k,s,s^{}}{}}[(\mathrm{e}^{\mathrm{i}k/3}a_{1:k,s}^{}a_{3:k,s^{}}`$ (A8)
$`\mathrm{e}^{\mathrm{i}k/3}a_{2:k,s}^{}a_{3:k,s^{}})\sigma _{ss^{}}^\lambda +\mathrm{H}.\mathrm{c}.],`$
$`h_{XA}^\lambda `$ $`=`$ $`a_{XA}^\lambda {\displaystyle \underset{k,s,s^{}}{}}(\mathrm{e}^{\mathrm{i}\pi /3}a_{1:k+\pi ,s}^{}a_{1:k,s^{}}`$ (A10)
$`+\mathrm{e}^{\mathrm{i}\pi /3}a_{2:k+\pi ,s}^{}a_{2:k,s^{}})\sigma _{ss^{}}^\lambda `$
$`+`$ $`b_{XA}^\lambda {\displaystyle \underset{k,s,s^{}}{}}a_{3:k+\pi ,s}^{}a_{3:k,s^{}}\sigma _{ss^{}}^\lambda `$ (A11)
$`+`$ $`c_{XA}^\lambda {\displaystyle \underset{k,s,s^{}}{}}[(\mathrm{e}^{\mathrm{i}(k+\pi )/3}a_{1:k+\pi ,s}^{}a_{3:k,s^{}}`$ (A13)
$`+\mathrm{e}^{\mathrm{i}(k+\pi )/3}a_{2:k+\pi ,s}^{}a_{3:k,s^{}})\sigma _{ss^{}}^\lambda +\mathrm{H}.\mathrm{c}.],`$
$`h_{XB}^\lambda `$ $`=`$ $`a_{XB}^\lambda {\displaystyle \underset{k,s,s^{}}{}}(\mathrm{e}^{\mathrm{i}\pi /3}a_{1:k+\pi ,s}^{}a_{1:k,s^{}}`$ (A15)
$`\mathrm{e}^{\mathrm{i}\pi /3}a_{2:k+\pi ,s}^{}a_{2:k,s^{}})\sigma _{ss^{}}^\lambda `$
$`+`$ $`b_{XB}^\lambda {\displaystyle \underset{k,s,s^{}}{}}[\mathrm{e}^{\mathrm{i}(k\pi )/3}a_{1:k+\pi ,s}^{}a_{2:k,s^{}}\sigma _{ss^{}}^\lambda +\mathrm{H}.\mathrm{c}.]`$ (A16)
$`+`$ $`c_{XB}^\lambda {\displaystyle \underset{k,s,s^{}}{}}[(\mathrm{e}^{\mathrm{i}(k+\pi )/3}a_{1:k+\pi ,s}^{}a_{3:k,s^{}}`$ (A18)
$`\mathrm{e}^{\mathrm{i}(k+\pi )/3}a_{2:k+\pi ,s}^{}a_{3:k,s^{}})\sigma _{ss^{}}^\lambda +\mathrm{H}.\mathrm{c}.],`$
where

$`a_{\mathrm{\Gamma }A}^0=\epsilon _\mathrm{M}{\displaystyle \frac{U_\mathrm{M}}{2}}+({\displaystyle \frac{U_\mathrm{M}}{2N}}+{\displaystyle \frac{2V_{\mathrm{MM}}}{N}}){\displaystyle \underset{k}{}}[\rho _{11}^0(\mathrm{\Gamma };k)`$ (A19)
$`+\rho _{22}^0(\mathrm{\Gamma };k)]+{\displaystyle \frac{4V_{\mathrm{MX}}}{N}}{\displaystyle }_k\rho _{33}^0(\mathrm{\Gamma };k),`$ (A20)
$`b_{\mathrm{\Gamma }A}^0=\epsilon _\mathrm{X}{\displaystyle \frac{U_\mathrm{X}}{2}}+{\displaystyle \frac{4V_{\mathrm{MX}}}{N}}{\displaystyle \underset{k}{}}[\rho _{11}^0(\mathrm{\Gamma };k)`$ (A21)
$`+\rho _{22}^0(\mathrm{\Gamma };k)]+{\displaystyle \frac{U_\mathrm{X}}{N}}{\displaystyle }_k\rho _{33}^0(\mathrm{\Gamma };k),`$ (A22)
$`c_{\mathrm{\Gamma }A}^0=t_{\mathrm{MM}}{\displaystyle \frac{2V_{\mathrm{MM}}}{N}}{\displaystyle \underset{k}{}}\mathrm{e}^{\mathrm{i}k/3}\rho _{12}^0(\mathrm{\Gamma };k),`$ (A23)
$`d_{\mathrm{\Gamma }A}^0=t_{\mathrm{MX}}{\displaystyle \frac{V_{\mathrm{MX}}}{N}}{\displaystyle \underset{k}{}}[\mathrm{e}^{\mathrm{i}k/3}\rho _{13}^0(\mathrm{\Gamma };k)`$ (A24)
$`+\mathrm{e}^{\mathrm{i}k/3}\rho _{23}^0(\mathrm{\Gamma };k)],`$ (A25)
$`a_{\mathrm{\Gamma }B}^0=({\displaystyle \frac{U_\mathrm{M}}{2N}}{\displaystyle \frac{2V_{\mathrm{MM}}}{N}}{\displaystyle \frac{\beta ^2}{KN}}){\displaystyle \underset{k}{}}[\rho _{11}^0(\mathrm{\Gamma };k)`$ (A26)
$`\rho _{22}^0(\mathrm{\Gamma };k)]+{\displaystyle \frac{2\alpha \beta }{KN}}{\displaystyle }_k[\mathrm{e}^{\mathrm{i}k/3}\rho _{13}^0(\mathrm{\Gamma };k)`$ (A27)
$`\mathrm{e}^{\mathrm{i}k/3}\rho _{23}^0(\mathrm{\Gamma };k)],`$ (A28)
$`b_{\mathrm{\Gamma }B}^0=({\displaystyle \frac{V_{\mathrm{MX}}}{N}}{\displaystyle \frac{2\alpha ^2}{KN}}){\displaystyle \underset{k}{}}[\mathrm{e}^{\mathrm{i}k/3}\rho _{13}^0(\mathrm{\Gamma };k)`$ (A29)
$`\mathrm{e}^{\mathrm{i}k/3}\rho _{23}^0(\mathrm{\Gamma };k)]+{\displaystyle \frac{\alpha \beta }{KN}}{\displaystyle }_k[\rho _{11}^0(\mathrm{\Gamma };k)`$ (A30)
$`\rho _{22}^0(\mathrm{\Gamma };k)],`$ (A31)
$`a_{XA}^0=({\displaystyle \frac{U_\mathrm{M}}{2N}}+{\displaystyle \frac{2V_{\mathrm{MM}}}{N}}{\displaystyle \frac{\beta ^2}{KN}}){\displaystyle \underset{k}{}}[\mathrm{e}^{\mathrm{i}\pi /3}\rho _{11}^0(X;k)`$ (A32)
$`+\mathrm{e}^{\mathrm{i}\pi /3}\rho _{22}^0(X;k)]+{\displaystyle \frac{4V_{\mathrm{MX}}}{N}}{\displaystyle }_k\rho _{33}^0(X,k)`$ (A33)
$`+{\displaystyle \frac{2\alpha \beta }{KN}}{\displaystyle \underset{k}{}}\left[\mathrm{e}^{\mathrm{i}k/3}\rho _{13}^0(X;k)+\mathrm{e}^{\mathrm{i}k/3}\rho _{23}^0(X;k)\right],`$ (A34)
$`b_{XA}^0={\displaystyle \frac{4V_{\mathrm{MX}}}{N}}{\displaystyle \underset{k}{}}\left[\mathrm{e}^{\mathrm{i}\pi /3}\rho _{11}^0(X;k)+\mathrm{e}^{\mathrm{i}\pi /3}\rho _{22}^0(X;k)\right]`$ (A35)
$`+{\displaystyle \frac{U_\mathrm{X}}{N}}{\displaystyle \underset{k}{}}\rho _{33}^0(X;k),`$ (A36)
$`c_{XA}^0=({\displaystyle \frac{V_{\mathrm{MX}}}{N}}+{\displaystyle \frac{2\alpha ^2}{KN}}){\displaystyle \underset{k}{}}[\mathrm{e}^{\mathrm{i}k/3}\rho _{13}^0(X;k)`$ (A37)
$`+\mathrm{e}^{\mathrm{i}k/3}\rho _{23}^0(X;k)]+{\displaystyle \frac{\alpha \beta }{KN}}{\displaystyle }_k[\mathrm{e}^{\mathrm{i}\pi /3}\rho _{11}^0(X;k)`$ (A38)
$`+\mathrm{e}^{\mathrm{i}\pi /3}\rho _{22}^0(X;k)],`$ (A39)
$`a_{XB}^0=({\displaystyle \frac{U_\mathrm{M}}{2N}}{\displaystyle \frac{2V_{\mathrm{MM}}}{N}}{\displaystyle \frac{\beta ^2}{KN}}){\displaystyle \underset{k}{}}[\mathrm{e}^{\mathrm{i}\pi /3}\rho _{11}^0(X;k)`$ (A40)
$`\mathrm{e}^{\mathrm{i}\pi /3}\rho _{22}^0(X;k)]+{\displaystyle \frac{2\alpha \beta }{KN}}{\displaystyle }_k[\mathrm{e}^{\mathrm{i}k/3}\rho _{13}^0(X;k)`$ (A41)
$`\mathrm{e}^{\mathrm{i}k/3}\rho _{23}^0(X;k)],`$ (A42)
$`b_{XB}^0={\displaystyle \frac{2V_{\mathrm{MM}}}{N}}{\displaystyle \underset{k}{}}\mathrm{e}^{\mathrm{i}(k\pi )/3}\rho _{12}^0(X;B),`$ (A43)
$`c_{XB}^0=({\displaystyle \frac{V_{\mathrm{MX}}}{N}}+{\displaystyle \frac{2\alpha ^2}{KN}}){\displaystyle \underset{k}{}}[\mathrm{e}^{\mathrm{i}k/3}\rho _{13}^0(X;k)`$ (A44)
$`\mathrm{e}^{\mathrm{i}k/3}\rho _{23}^0(X;k)]+{\displaystyle \frac{\alpha \beta }{KN}}{\displaystyle }_k[\mathrm{e}^{\mathrm{i}\pi /3}\rho _{11}^0(X;k)`$ (A45)
$`\mathrm{e}^{\mathrm{i}\pi /3}\rho _{22}^0(X;k)],`$ (A46)
$`a_{\mathrm{\Gamma }A}^z={\displaystyle \frac{U_\mathrm{M}}{2N}}{\displaystyle \underset{k}{}}\left[\rho _{11}^z(\mathrm{\Gamma };k)+\rho _{22}^z(\mathrm{\Gamma };k)\right],`$ (A47)
$`b_{\mathrm{\Gamma }A}^z={\displaystyle \frac{U_\mathrm{X}}{N}}{\displaystyle \underset{k}{}}\rho _{33}^z(\mathrm{\Gamma };k),`$ (A48)
$`c_{\mathrm{\Gamma }A}^z={\displaystyle \frac{2V_{\mathrm{MM}}}{N}}{\displaystyle \underset{k}{}}\mathrm{e}^{\mathrm{i}k/3}\rho _{12}^z(\mathrm{\Gamma };k),`$ (A49)
$`d_{\mathrm{\Gamma }A}^z={\displaystyle \frac{V_{\mathrm{MX}}}{N}}{\displaystyle \underset{k}{}}\left[\mathrm{e}^{\mathrm{i}k/3}\rho _{13}^z(\mathrm{\Gamma };k)+\mathrm{e}^{\mathrm{i}k/3}\rho _{23}^z(\mathrm{\Gamma };k)\right],`$ (A50)
(A51)
$`a_{\mathrm{\Gamma }B}^z={\displaystyle \frac{U_\mathrm{M}}{2N}}{\displaystyle \underset{k}{}}\left[\rho _{11}^z(\mathrm{\Gamma };k)\rho _{22}^z(\mathrm{\Gamma };k)\right],`$ (A52)
$`b_{\mathrm{\Gamma }B}^z={\displaystyle \frac{V_{\mathrm{MX}}}{N}}{\displaystyle \underset{k}{}}\left[\mathrm{e}^{\mathrm{i}k/3}\rho _{13}^z(\mathrm{\Gamma };k)\mathrm{e}^{\mathrm{i}k/3}\rho _{23}^z(\mathrm{\Gamma };k)\right],`$ (A53)
(A54)
$`a_{XA}^z={\displaystyle \frac{U_\mathrm{M}}{2N}}{\displaystyle \underset{k}{}}\left[\mathrm{e}^{\mathrm{i}\pi /3}\rho _{11}^z(X;k)+\mathrm{e}^{\mathrm{i}\pi /3}\rho _{22}^z(X;k)\right],`$ (A55)
$`b_{XA}^z={\displaystyle \frac{U_\mathrm{X}}{N}}{\displaystyle \underset{k}{}}\rho _{33}^z(X;k),`$ (A56)
$`c_{XA}^z={\displaystyle \frac{V_{\mathrm{MX}}}{N}}{\displaystyle \underset{k}{}}\left[\mathrm{e}^{\mathrm{i}k/3}\rho _{13}^z(X;k)+\mathrm{e}^{\mathrm{i}k/3}\rho _{23}^z(X;k)\right],`$ (A57)
(A58)
$`a_{XB}^z={\displaystyle \frac{U_\mathrm{M}}{2N}}{\displaystyle \underset{k}{}}\left[\mathrm{e}^{\mathrm{i}\pi /3}\rho _{11}^z(X;k)\mathrm{e}^{\mathrm{i}\pi /3}\rho _{22}^z(X;k)\right],`$ (A59)
$`b_{XB}^z={\displaystyle \frac{V_{\mathrm{MM}}}{N}}{\displaystyle \underset{k}{}}\mathrm{e}^{\mathrm{i}(k\pi )/3}\rho _{12}^z(X;k),`$ (A60)
$`c_{XB}^z={\displaystyle \frac{V_{\mathrm{MX}}}{N}}{\displaystyle \underset{k}{}}\left[\mathrm{e}^{\mathrm{i}k/3}\rho _{13}^z(X;k)\mathrm{e}^{\mathrm{i}k/3}\rho _{23}^z(X;k)\right].`$ (A61)
(A62)
In obtaining the spatial-symmetry-definite order parameters (A25)-(A62), the lattice distortion has been described in terms of the electron density matrices so as to minimize the Hartree-Fock energy

$`_{\mathrm{HF}}=2{\displaystyle \underset{i,j}{}}{\displaystyle \underset{k}{}}i:k|t|j:k\rho _{ji}^0(\mathrm{\Gamma };k)`$ (A63)
$`+2{\displaystyle \underset{i,j}{}}{\displaystyle \underset{k}{}}i:k+\pi |t|j:k\rho _{ji}^0(X;k)`$ (A64)
$`+{\displaystyle \underset{i,j,m,n}{}}{\displaystyle \underset{k,k^{}}{}}(2i:k;m:k^{}|v|j:k;n:k^{}`$ (A65)
$`i:k;m:k^{}|v|n:k^{};j:k)\rho _{ji}^0(\mathrm{\Gamma };k)\rho _{nm}^0(\mathrm{\Gamma };k^{})`$ (A66)
$`+{\displaystyle \underset{i,j,m,n}{}}{\displaystyle \underset{k,k^{}}{}}(2i:k+\pi ;m:k^{}|v|j:k;n:k^{}+\pi `$ (A67)
$`i:k+\pi ;m:k^{}|v|n:k^{}+\pi ;j:k)`$ (A68)
$`\times \mathrm{e}^{(2\pi /3)i\delta _{m1}}\mathrm{e}^{(2\pi /3)i\delta _{m2}}\rho _{ji}^0(\mathrm{\Gamma };k)\rho _{nm}^0(\mathrm{\Gamma };k^{}+\pi )`$ (A69)
$`{\displaystyle \underset{i,j,m,n}{}}{\displaystyle \underset{k,k^{}}{}}i:k;m:k^{}|v|n:k^{};j:k`$ (A70)
$`\times \rho _{ji}^z(\mathrm{\Gamma },k)\rho _{nm}^z(\mathrm{\Gamma },k^{})`$ (A71)
$`{\displaystyle \underset{i,j,m,n}{}}{\displaystyle \underset{k,k^{}}{}}i:k+\pi ;m:k^{}|v|n:k^{}+\pi ;j:k`$ (A72)
$`\times \mathrm{e}^{(2\pi /3)i\delta _{m1}}\mathrm{e}^{(2\pi /3)i\delta _{m2}}\rho _{ji}^z(\mathrm{\Gamma },k)\rho _{nm}^z(\mathrm{\Gamma },k^{}+\pi )`$ (A73)
$`+{\displaystyle \frac{K}{2}}{\displaystyle \underset{q=0,\pi }{}}\left[\left(u_{3:q}\mathrm{e}^{\mathrm{i}q/3}u_{1:q}\right)^2+\left(u_{3:q}\mathrm{e}^{\mathrm{i}q/3}u_{2:q}\right)^2\right].`$ (A74)
(A75)
Considering that the density matrices should possess the same symmetry properties as the irreducible Hamiltonian to which they belong, the coefficients (A25)-(A62) all turn out to be real.

## B Characterization of the Density-Wave Solutions

(a) $`\mathrm{\Gamma }A\stackrel{ˇ}{S}^0\stackrel{ˇ}{T}^0`$

$`d_{1:n}=d_{2:n}={\displaystyle \frac{2}{N}}{\displaystyle \underset{k}{}}\overline{\rho }_{11}^0(\mathrm{\Gamma };k),`$ (B1)
$`d_{3:n}={\displaystyle \frac{2}{N}}{\displaystyle \underset{k}{}}\overline{\rho }_{33}^0(\mathrm{\Gamma };k),`$ (B2)
$`p_{1:n;2:n1}={\displaystyle \frac{2}{N}}{\displaystyle \underset{k}{}}\left[\overline{\rho }_{12}^0(\mathrm{\Gamma };k)\mathrm{cos}{\displaystyle \frac{k}{3}}\stackrel{~}{\rho }_{12}^0(\mathrm{\Gamma };k)\mathrm{sin}{\displaystyle \frac{k}{3}}\right],`$ (B3)
$`p_{1:n;3:n}=p_{2:n;3:n}`$ (B4)
$`={\displaystyle \frac{2}{N}}{\displaystyle \underset{k}{}}\left[\overline{\rho }_{13}^0(\mathrm{\Gamma };k)\mathrm{cos}{\displaystyle \frac{k}{3}}+\stackrel{~}{\rho }_{13}^0(\mathrm{\Gamma };k)\mathrm{sin}{\displaystyle \frac{k}{3}}\right].`$ (B5)
(b) $`\mathrm{\Gamma }B\stackrel{ˇ}{S}^0\stackrel{ˇ}{T}^0`$

$`d_{i:n}={\displaystyle \frac{2}{N}}{\displaystyle \underset{k}{}}\overline{\rho }_{ii}^0(\mathrm{\Gamma };k)(i=1,2,3),`$ (B6)
$`p_{1:n;2:n1}={\displaystyle \frac{2}{N}}{\displaystyle \underset{k}{}}\left[\overline{\rho }_{12}^0(\mathrm{\Gamma };k)\mathrm{cos}{\displaystyle \frac{k}{3}}\stackrel{~}{\rho }_{12}^0(\mathrm{\Gamma };k)\mathrm{sin}{\displaystyle \frac{k}{3}}\right],`$ (B7)
$`p_{1:n;3:n}={\displaystyle \frac{2}{N}}{\displaystyle \underset{k}{}}\left[\overline{\rho }_{13}^0(\mathrm{\Gamma };k)\mathrm{cos}{\displaystyle \frac{k}{3}}+\stackrel{~}{\rho }_{13}^0(\mathrm{\Gamma };k)\mathrm{sin}{\displaystyle \frac{k}{3}}\right],`$ (B8)
$`p_{2:n;3:n}={\displaystyle \frac{2}{N}}{\displaystyle \underset{k}{}}\left[\overline{\rho }_{23}^0(\mathrm{\Gamma };k)\mathrm{cos}{\displaystyle \frac{k}{3}}\stackrel{~}{\rho }_{23}^0(\mathrm{\Gamma };k)\mathrm{sin}{\displaystyle \frac{k}{3}}\right],`$ (B9)
$`u_{3:n}={\displaystyle \frac{\beta }{KN}}{\displaystyle \underset{k}{}}\left[\overline{\rho }_{11}^0(\mathrm{\Gamma };k)\overline{\rho }_{22}^0(\mathrm{\Gamma };k)\right]`$ (B10)
$`{\displaystyle \frac{2\alpha }{KN}}{\displaystyle \underset{k}{}}[\overline{\rho }_{13}^0(\mathrm{\Gamma };k)\mathrm{cos}{\displaystyle \frac{k}{3}}+\stackrel{~}{\rho }_{13}^0(\mathrm{\Gamma };k)\mathrm{sin}{\displaystyle \frac{k}{3}}`$ (B11)
$`\overline{\rho }_{23}^0(\mathrm{\Gamma };k)\mathrm{cos}{\displaystyle \frac{k}{3}}+\stackrel{~}{\rho }_{23}^0(\mathrm{\Gamma };k)\mathrm{sin}{\displaystyle \frac{k}{3}}].`$ (B12)
(c) $`XA\stackrel{ˇ}{S}^0\stackrel{ˇ}{T}^0`$

$`d_{1:n}=d_{2:n}={\displaystyle \frac{2}{N}}{\displaystyle \underset{k}{}}\overline{\rho }_{11}^0(\mathrm{\Gamma };k)`$ (B13)
$`+{\displaystyle \frac{2(1)^n}{N}}{\displaystyle \underset{k}{}}\left[\overline{\rho }_{11}^0(X;k)\mathrm{cos}{\displaystyle \frac{\pi }{3}}\stackrel{~}{\rho }_{11}^0(X;k)\mathrm{sin}{\displaystyle \frac{\pi }{3}}\right],`$ (B14)
$`d_{3:n}={\displaystyle \frac{2}{N}}{\displaystyle \underset{k}{}}\overline{\rho }_{33}^0(\mathrm{\Gamma };k)+{\displaystyle \frac{2(1)^n}{N}}{\displaystyle \underset{k}{}}\overline{\rho }_{33}^0(X;k),`$ (B15)
$`p_{1:n;2:n1}={\displaystyle \frac{2}{N}}{\displaystyle \underset{k}{}}\left[\overline{\rho }_{12}^0(\mathrm{\Gamma };k)\mathrm{cos}{\displaystyle \frac{k}{3}}\stackrel{~}{\rho }_{12}^0(\mathrm{\Gamma };k)\mathrm{sin}{\displaystyle \frac{k}{3}}\right],`$ (B16)
$`p_{1:n;3:n}=p_{2:n;3:n}`$ (B17)
$`={\displaystyle \frac{2}{N}}{\displaystyle \underset{k}{}}\left[\overline{\rho }_{13}^0(\mathrm{\Gamma };k)\mathrm{cos}{\displaystyle \frac{k}{3}}+\stackrel{~}{\rho }_{13}^0(\mathrm{\Gamma };k)\mathrm{sin}{\displaystyle \frac{k}{3}}\right]`$ (B18)
$`+{\displaystyle \frac{2(1)^n}{N}}{\displaystyle \underset{k}{}}\left[\overline{\rho }_{13}^0(X;k)\mathrm{cos}{\displaystyle \frac{k}{3}}+\stackrel{~}{\rho }_{13}^0(X;k)\mathrm{sin}{\displaystyle \frac{k}{3}}\right],`$ (B19)
$`u_{1:n}=u_{2:n}=(1)^n`$ (B20)
$`\times \{{\displaystyle \frac{4\alpha }{KN}}{\displaystyle \underset{k}{}}[\overline{\rho }_{13}^0(X;k)\mathrm{cos}{\displaystyle \frac{k}{3}}+\stackrel{~}{\rho }_{13}^0(X;k)\mathrm{sin}{\displaystyle \frac{k}{3}}]`$ (B21)
$`{\displaystyle \frac{2\beta }{KN}}{\displaystyle \underset{k}{}}[\overline{\rho }_{13}^0(X;k)\mathrm{cos}{\displaystyle \frac{\pi }{3}}\stackrel{~}{\rho }_{13}^0(X;k)\mathrm{sin}{\displaystyle \frac{\pi }{3}}]\}.`$ (B22)
(d) $`XB\stackrel{ˇ}{S}^0\stackrel{ˇ}{T}^0`$

$`d_{1:n}={\displaystyle \frac{2}{N}}{\displaystyle \underset{k}{}}\overline{\rho }_{11}^0(\mathrm{\Gamma };k)`$ (B23)
$`+{\displaystyle \frac{2(1)^n}{N}}{\displaystyle \underset{k}{}}\left[\overline{\rho }_{11}^0(X;k)\mathrm{cos}{\displaystyle \frac{\pi }{3}}\stackrel{~}{\rho }_{11}^0(X;k)\mathrm{sin}{\displaystyle \frac{\pi }{3}}\right],`$ (B24)
$`d_{2:n}={\displaystyle \frac{2}{N}}{\displaystyle \underset{k}{}}\overline{\rho }_{11}^0(\mathrm{\Gamma };k)`$ (B25)
$`{\displaystyle \frac{2(1)^n}{N}}{\displaystyle \underset{k}{}}\left[\overline{\rho }_{11}^0(X;k)\mathrm{cos}{\displaystyle \frac{\pi }{3}}\stackrel{~}{\rho }_{11}^0(X;k)\mathrm{sin}{\displaystyle \frac{\pi }{3}}\right],`$ (B26)
$`d_{3:n}={\displaystyle \frac{2}{N}}{\displaystyle \underset{k}{}}\overline{\rho }_{33}^0(\mathrm{\Gamma };k),`$ (B27)
$`p_{1:n;2:n1}={\displaystyle \frac{2}{N}}{\displaystyle \underset{k}{}}\left[\overline{\rho }_{12}^0(\mathrm{\Gamma };k)\mathrm{cos}{\displaystyle \frac{k}{3}}\stackrel{~}{\rho }_{12}^0(\mathrm{\Gamma };k)\mathrm{sin}{\displaystyle \frac{k}{3}}\right]`$ (B28)
$`{\displaystyle \frac{2(1)^n}{N}}{\displaystyle \underset{k}{}}`$ (B29)
$`\times \left[\overline{\rho }_{12}^0(X;k)\mathrm{cos}{\displaystyle \frac{k\pi }{3}}\stackrel{~}{\rho }_{12}^0(X;k)\mathrm{sin}{\displaystyle \frac{k\pi }{3}}\right],`$ (B30)
$`p_{1:n;3:n}={\displaystyle \frac{2}{N}}{\displaystyle \underset{k}{}}\left[\overline{\rho }_{13}^0(\mathrm{\Gamma };k)\mathrm{cos}{\displaystyle \frac{k}{3}}+\stackrel{~}{\rho }_{13}^0(\mathrm{\Gamma };k)\mathrm{sin}{\displaystyle \frac{k}{3}}\right]`$ (B31)
$`+{\displaystyle \frac{2(1)^n}{N}}{\displaystyle \underset{k}{}}\left[\overline{\rho }_{13}^0(X;k)\mathrm{cos}{\displaystyle \frac{k}{3}}+\stackrel{~}{\rho }_{13}^0(X;k)\mathrm{sin}{\displaystyle \frac{k}{3}}\right],`$ (B32)
$`p_{2:n;3:n}={\displaystyle \frac{2}{N}}{\displaystyle \underset{k}{}}\left[\overline{\rho }_{13}^0(\mathrm{\Gamma };k)\mathrm{cos}{\displaystyle \frac{k}{3}}+\stackrel{~}{\rho }_{13}^0(\mathrm{\Gamma };k)\mathrm{sin}{\displaystyle \frac{k}{3}}\right]`$ (B33)
$`{\displaystyle \frac{2(1)^n}{N}}{\displaystyle \underset{k}{}}\left[\overline{\rho }_{13}^0(X;k)\mathrm{cos}{\displaystyle \frac{k}{3}}+\stackrel{~}{\rho }_{13}^0(X;k)\mathrm{sin}{\displaystyle \frac{k}{3}}\right],`$ (B34)
$`u_{3:n}=(1)^n`$ (B35)
$`\times \{{\displaystyle \frac{4\alpha }{KN}}{\displaystyle \underset{k}{}}[\overline{\rho }_{13}^0(X;k)\mathrm{cos}{\displaystyle \frac{k}{3}}+\stackrel{~}{\rho }_{13}^0(X;k)\mathrm{sin}{\displaystyle \frac{k}{3}}]`$ (B36)
$`{\displaystyle \frac{2\beta }{KN}}{\displaystyle \underset{k}{}}[\overline{\rho }_{13}^0(X;k)\mathrm{cos}{\displaystyle \frac{\pi }{3}}\stackrel{~}{\rho }_{13}^0(X;k)\mathrm{sin}{\displaystyle \frac{\pi }{3}}]\}.`$ (B37)
(e) $`\mathrm{\Gamma }A\stackrel{ˇ}{S}^1\stackrel{ˇ}{T}^1`$

$`s_{1:n}^z=s_{2:n}^z={\displaystyle \frac{1}{N}}{\displaystyle \underset{k}{}}\overline{\rho }_{11}^z(\mathrm{\Gamma };k),`$ (B38)
$`s_{3:n}^z={\displaystyle \frac{1}{N}}{\displaystyle \underset{k}{}}\overline{\rho }_{33}^z(\mathrm{\Gamma };k),`$ (B39)
$`t_{1:n;2:n1}^z={\displaystyle \frac{1}{N}}{\displaystyle \underset{k}{}}\left[\overline{\rho }_{12}^z(\mathrm{\Gamma };k)\mathrm{cos}{\displaystyle \frac{k}{3}}\stackrel{~}{\rho }_{12}^z(\mathrm{\Gamma };k)\mathrm{sin}{\displaystyle \frac{k}{3}}\right],`$ (B40)
$`t_{1:n;3:n}^z=t_{2:n;3:n}^z`$ (B41)
$`={\displaystyle \frac{1}{N}}{\displaystyle \underset{k}{}}\left[\overline{\rho }_{13}^z(\mathrm{\Gamma };k)\mathrm{cos}{\displaystyle \frac{k}{3}}+\stackrel{~}{\rho }_{13}^z(\mathrm{\Gamma };k)\mathrm{sin}{\displaystyle \frac{k}{3}}\right].`$ (B42)
(f) $`\mathrm{\Gamma }B\stackrel{ˇ}{S}^1\stackrel{ˇ}{T}^1`$

$`s_{1:n}^z=s_{2:n}^z={\displaystyle \frac{1}{N}}{\displaystyle \underset{k}{}}\overline{\rho }_{11}^z(\mathrm{\Gamma };k),s_{3:n}^z=0,`$ (B43)
$`t_{1:n;2:n1}^z=0,t_{1:n;3:n}^z=t_{2:n;3:n}^z`$ (B44)
$`={\displaystyle \frac{1}{N}}{\displaystyle \underset{k}{}}\left[\overline{\rho }_{13}^z(\mathrm{\Gamma };k)\mathrm{cos}{\displaystyle \frac{k}{3}}+\stackrel{~}{\rho }_{13}^z(\mathrm{\Gamma };k)\mathrm{sin}{\displaystyle \frac{k}{3}}\right].`$ (B45)
(g) $`XA\stackrel{ˇ}{S}^1\stackrel{ˇ}{T}^1`$

$`s_{1:n}^z=s_{2:n}^z`$ (B46)
$`={\displaystyle \frac{(1)^n}{N}}{\displaystyle \underset{k}{}}\left[\overline{\rho }_{11}^z(X;k)\mathrm{cos}{\displaystyle \frac{\pi }{3}}\stackrel{~}{\rho }_{11}^z(X;k)\mathrm{sin}{\displaystyle \frac{\pi }{3}}\right],`$ (B47)
$`s_{3:n}^z={\displaystyle \frac{(1)^n}{N}}{\displaystyle \underset{k}{}}\overline{\rho }_{33}^z(X;k),`$ (B48)
$`t_{1:n;2:n1}^z=0,t_{1:n;3:n}^z=t_{2:n;3:n}^z`$ (B49)
$`={\displaystyle \frac{(1)^n}{N}}{\displaystyle \underset{k}{}}\left[\overline{\rho }_{13}^z(X;k)\mathrm{cos}{\displaystyle \frac{k}{3}}+\stackrel{~}{\rho }_{13}^z(X;k)\mathrm{sin}{\displaystyle \frac{k}{3}}\right].`$ (B50)
(h) $`XB\stackrel{ˇ}{S}^1\stackrel{ˇ}{T}^1`$

$`s_{3:n}^z=0,s_{1:n}^z=s_{2:n}^z`$ (B51)
$`={\displaystyle \frac{(1)^n}{N}}{\displaystyle \underset{k}{}}\left[\overline{\rho }_{11}^z(X;k)\mathrm{cos}{\displaystyle \frac{\pi }{3}}\stackrel{~}{\rho }_{11}^z(X;k)\mathrm{sin}{\displaystyle \frac{\pi }{3}}\right],`$ (B52)
$`t_{1:n;2:n1}^z={\displaystyle \frac{(1)^n}{N}}{\displaystyle \underset{k}{}}`$ (B53)
$`\times \left[\overline{\rho }_{12}^z(X;k)\mathrm{cos}{\displaystyle \frac{k\pi }{3}}\stackrel{~}{\rho }_{12}^z(X;k)\mathrm{sin}{\displaystyle \frac{k\pi }{3}}\right],`$ (B54)
$`t_{1:n;3:n}^z=t_{2:n;3:n}^z`$ (B55)
$`={\displaystyle \frac{(1)^n}{N}}{\displaystyle \underset{k}{}}\left[\overline{\rho }_{13}^z(X;k)\mathrm{cos}{\displaystyle \frac{k}{3}}+\stackrel{~}{\rho }_{13}^z(X;k)\mathrm{sin}{\displaystyle \frac{k}{3}}\right].`$ (B56)


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# 1 Introduction

## 1 Introduction

The Bekenstein bound  for the ratio of the entropy $`S`$ to the total energy $`E`$ of a closed physical system444For recent discussions on general entropy bounds of physical systems see  and references therein. that fits in a sphere in three spatial dimensions reads

$$\frac{S}{2\pi RE}1,$$
(1)
where $`R`$ denotes the radius of the sphere. Despite many efforts, the microscopic origin of the bound remains elusive. A recent interesting development is Verlinde’s observation  that CFTs possessing AdS duals satisfy a version of the bound (1). One firstly observes that for general CFTs on $`\times S^{D1}`$, with the radius of $`S^{D1}`$ being $`R`$, the product $`ER`$ is independent of the total spatial volume $`V`$. If one defines the sub-extensive part $`E_C`$ of the total energy through the scaling property $`E_C(\lambda S,\lambda V)=\lambda ^{1\frac{2}{D1}}E_C(S,V)`$ and $`E=E_{ext}+\frac{1}{2}E_C`$, it follows that555The same result can be obtained using the equation of state $`p=E/V(D1)`$, where $`p`$ is the pressure, that follows from the tracelessness of the energy momentum tensor in a CFT.

$$E_C=DE(D1)TS.$$
(2)
The observation of Verlinde is that for strongly coupled CFTs with AdS duals the entropy is given by a generalized Cardy formula

$$S=\frac{2\pi R}{D1}\sqrt{E_C(2EE_C)}.$$
(3)
To show this, one employs the results for the entropy and total energy of the corresponding $`D`$-dimensional CFT that fits into a $`(D1)`$-dimensional sphere at finite temperature . These are obtained by virtue of holography  from the corresponding thermodynamical quantities of a $`(D+1)`$-dimensional Schwarzschild AdS black hole. From (3) one obtains a bound similar to (1), namely666Henceforth we call (4) the Verlinde CFT bound to avoid confusion with the cosmological entropy bound suggested by Verlinde also in .

$$\frac{S}{2\pi RE}\frac{1}{D1}.$$
(4)
In view of the above developments, a natural question arising is whether there exists a microscopic derivation of Verlinde’s formula (3) within the thermodynamics of CFTs. This question could be checked in the context of CFTs whose microscopic thermodynamics is well understood, such as free CFTs on $`\times S^{D1}`$. The relevant calculations for dimensions $`D=4,6`$ were recently undertaken by Kutasov and Larsen  (See also . A detailed analysis of four-dimensional thermal CFTs appeared in .) They computed the high temperature limits of various partition functions on $`S^1\times S^{D1}`$, from which all thermodynamical quantities follow. It was then shown that the Verlinde CFT bound (4) is violated for free CFTs.

In the present work we perform a further analysis of the results in  for free CFTs in dimensions $`D=4,6`$. We find that for the specific cases of $`𝒩=4`$ $`U(N)`$ SYM theory in $`D=4`$ and the $`(2,0)`$ tensor multiplet in $`D=6`$, the ratio of the entropy to the total energy is bounded from above, however the corresponding bounds are less stringent than (4). We show that general bounds for the ratio of the entropy to the total energy in $`D`$-dimensional CFTs arise naturally under the requirement of monotonicity properties with respect to temperature changes of a generalized $`C`$-function. This generalized $`C`$-function is related to the sub-extensive part (2) of the total energy. Although bounds for the ratio of the entropy to the total energy seem to arise quite generically in CFTs, their exact values depend on the details of the underlying CFT, e.g. it seems that the bounds become more stringent as one goes from weak to strong coupling.

Next we turn our attention to strongly coupled CFTs with AdS duals. We show that the Verlinde formula (3) remains valid also in the case of strongly coupled CFTs in a rotating Einstein universe. We then point out an intriguing resemblance of the formulas of $`(D+1)`$-dimensional AdS black hole thermodynamics to corresponding formulas in the thermodynamics of two-dimensional CFTs. Particularly interesting is the fact that the entropy of the black hole resembles the $`C`$-function of a two-dimensional system. Motivated by this, we suggest a simple scaling form for the free energy of a $`D`$-dimensional CFT in a space with finite extent at finite temperature. Requiring then that the entropy of such a theory is given by a generalization of the two-dimensional entropy, leads to a simple differential equation whose solution yields a finite-size correlation length that turns out to coincide with the horizon distance of $`(D+1)`$-dimensional AdS black holes.

The paper is organized as follows. In section 2 we analyze the thermodynamics of free CFTs on $`S^1\times S^{D1}`$ and show that for $`D=4`$, $`𝒩=4`$ SYM theory and for the $`(2,0)`$ tensor multiplet the ratio of the entropy to the total energy is bounded from above. We also show that bounds for the ratio of the entropy to the total energy arise naturally in CFTs if certain monotonicity properties of a generalized $`C`$-function are assumed. In section 3 we show that the Verlinde formula (3) is valid for strongly coupled CFTs in a rotating Einstein universe, which are dual to Kerr-AdS black holes. We then suggest simple scaling forms for the free energy and the entropy of $`D`$-dimensional strongly coupled CFTs at finite temperature that reproduce the results of AdS black hole thermodynamics. In section 4 we conclude and discuss some implications of our results for cosmology, as well as possible further developments of our ideas.

## 2 Entropy bounds in CFTs at finite temperature

### 2.1 General results and free CFTs

In this section, we discuss the thermodynamics of conformal field theories. For a general statistical mechanical system, one defines the partition function (we put $`k=\mathrm{}=1`$)

$$Z=\underset{E}{}\rho (E)e^{E/T},$$
(5)
where $`\rho (E)`$ is the number of states with energy $`E`$. In general, (5) can be evaluated using a saddle point approximation. The exponent is stationary when

$$dS=\frac{dE}{T},S=\mathrm{ln}\rho ,$$
(6)
where $`S`$ is the entropy of the system. This approximation is valid for a large number of degrees of freedom, i.e. if the underlying theory is a CFT with a large central charge. The free energy

$$F=T\mathrm{ln}Z,$$
(7)
at the saddle point is the exponent in (5),

$$F=ETS,$$
(8)
and on account of (6), the entropy is given by

$$S=\frac{F}{T}.$$
(9)
As an application, consider $`C`$ free massless bosons living on a three-dimensional spatial sphere of radius $`R`$ at finite temperature. The energy levels and corresponding degeneracies of the various modes are

$$E_n=\frac{n}{R},d_n=n^2.$$
(10)
Therefore, the partition function reads

$$Z_B^{(4)}=\underset{n=1}{\overset{\mathrm{}}{}}(1q^n)^{Cn^2},q=e^{2\pi \delta },\delta =\frac{1}{2\pi RT}.$$
(11)
To cast this into the form (5), we exploit the modular properties of the partition function $`Z_B^{(4)}`$. Using a Mellin transform, one obtains

$$Z_B^{(4)}=e^{\frac{\pi C}{360}\delta ^3}e^{\frac{\pi C}{120}\delta }𝒵,$$
(12)
where $`𝒵`$ is a slowly varying function (approximately constant) near the saddle point. Therefore, the free energy (7) in the saddle point approximation is

$$F_B^{(4)}R=\frac{C}{240}\left(\frac{1}{3}\delta ^4+1\right),$$
(13)
where we multiplied by the negative radius $`R`$ for convenience. The entropy and energy of the system are easily deduced from the thermodynamical relations (8) and (9),

$$S=\frac{\pi C}{90}\delta ^3,E=\frac{C}{240}\left(\delta ^41\right).$$
(14)
For comparison, in two dimensions, the partition function of $`C`$ free bosons is

$$Z_B^{(2)}=\underset{n=1}{\overset{\mathrm{}}{}}(1q^n)^C,$$
(15)
leading to the free energy

$$F_B^{(2)}R=\frac{C}{24}\left(\delta ^21\right),$$
(16)
while the entropy and energy read, respectively

$$S=\frac{\pi C}{6}\delta ^1,ER=\frac{C}{24}\left(\delta ^2+1\right).$$
(17)
We should point out that in this case there is a contribution from the zero modes of the form $`\delta ^{C/2}`$. This is a slowly varying function and does not contribute to the rapidly varying exponentials that comprise the free energy at the saddle point. The contribution of the zero modes becomes significant when the saddle-point approximation breaks down, for a small central charge.777We thank D. Kutasov for pointing out this to us. Here, we are interested in the large $`C`$ limit, so such contributions will be ignored.

Eq. (17) implies the Cardy formula

$$S=2\pi \sqrt{\frac{C}{6}\left(E\frac{C}{24}\right)},$$
(18)
and the Bekenstein bound (1) for the ratio

$$\frac{S}{2\pi ER}=\frac{2\delta }{1+\delta ^2}1.$$
(19)
The above results also hold for fermions, because the free energy for a fermion is $`F_F^{(2)}=\frac{1}{2}F_B^{(2)}`$.

Returning to four dimensions, we note from (14) that there is a transition point at $`\delta =1`$ where $`ER=0`$. At that point the ratio $`S/E`$ diverges because the entropy remains finite. Thus, it seems as if the ratio of the entropy to the total energy is not bounded for free bosons. Similar results hold for Weyl fermions and vector bosons. However, in systems with diverse mode species there is a chance that the above ratio is bounded. Consider the free energy of a system of $`N_B`$ bosons, $`N_F`$ Weyl fermions and $`N_V`$ vectors that reads

$$FR=a_4\delta ^4+a_2\delta ^2+a_0,$$
(20)
where

$$a_4=\frac{1}{720}(N_B+\frac{7}{4}N_F+2N_V),a_2=\frac{1}{24}(\frac{1}{4}N_F+2N_V),a_0=\frac{1}{240}(N_B+\frac{17}{4}N_F+22N_V),$$
(21)
satisfying the constraint $`3a_4=a_2+a_0`$. The entropy and energy are, respectively,

$$S=2\pi (4a_4\delta ^3+2a_2\delta ^1),ER=3a_4\delta ^4+a_2\delta ^2a_0.$$
(22)
The Bekenstein-Verlinde ratio is

$$\frac{S}{2\pi ER}=\delta \frac{4a_4+2a_2\delta ^2}{3a_4+a_2\delta ^2a_0\delta ^4}=\frac{2\delta }{1+\delta ^2}\frac{2a_4+a_2\delta ^2}{3a_4a_0\delta ^2}.$$
(23)
Remarkably, for the $`𝒩=4`$ SYM model, we have $`a_2=6a_4`$, which implies

$$\frac{S}{2\pi ER}=\frac{2}{3}\frac{2\delta }{1+\delta ^2}.$$
(24)
One might now think that (24) generally implies the bound $`S/(2\pi ER)2/3`$. However, we have to keep in mind that (20) and (22) are high temperature expansions and should not be trusted for large-$`\delta `$. Starting from high temperatures (small-$`\delta `$), there is a critical point at which both $`S`$ and $`ER`$ vanish for

$$\delta _c^2=\frac{2a_4}{a_2}=\frac{1}{3}.$$
(25)
We should not expect that (23) makes sense for $`\delta \delta _c`$. Nevertheless, for $`\delta \delta _c`$, we obtain the bound

$$\frac{S}{2\pi ER}\frac{\sqrt{3}}{3},$$
(26)
which is weaker than the Verlinde CFT bound (4) $`S/(2\pi ER)1/3`$.

It is perhaps worth mentioning that if one imposes periodic boundary conditions on the gaugino, as suggested by Tseytlin  to account for the disagreement on the number of degrees of freedom between the weak and strong coupling regimes, the above results still hold. Indeed, the partition function for a gaugino with periodic boundary conditions is

$$\stackrel{~}{Z}_F=\underset{n=0}{\overset{\mathrm{}}{}}(1q^{n+1/2})^{2n(n+1)},$$
(27)
which leads to the free energy for $`\stackrel{~}{N}_F`$ gauginos,

$$\stackrel{~}{F}R=\stackrel{~}{N}_F(\stackrel{~}{a}_4\delta ^4+\stackrel{~}{a}_2\delta ^2+\stackrel{~}{a}_0),$$
(28)
where

$$\stackrel{~}{a}_4=\frac{1}{360},\stackrel{~}{a}_2=\frac{1}{48},\stackrel{~}{a}_0=\frac{7}{240}.$$
(29)
For the $`𝒩=4`$ SYM model with such gauginos, the coefficients of the free energy (20) still satisfy $`3a_4^{}=a_2^{}+a_0^{}`$ and the ratio $`a_2^{}/a_4^{}`$ is unchanged

$$\frac{a_2^{}}{a_4^{}}=30\frac{\frac{1}{4}N_F\frac{1}{2}\stackrel{~}{N}_F+2N_V}{N_B+\frac{7}{4}N_F2\stackrel{~}{N}_F+2N_V}=6.$$
(30)
Thus, the only effect of imposing periodic boundary conditions on the gauginos is the reduction of the free energy by an overall factor of $`a_4^{}/a_4=3/4`$.

Next we turn to the $`(2,0)`$ tensor multiplet in $`D=6`$. The free energy is

$$FR=a_6\delta ^6+a_4\delta ^4+a_2\delta ^2+a_0.$$
(31)
The entropy is given by

$$\frac{S}{2\pi }=TSR\delta =T\frac{(FR)}{T}\delta =6a_6\delta ^5+4a_4\delta ^3+2a_2\delta ^1,$$
(32)
and the energy by

$$ER=5a_6\delta ^6+3a_4\delta ^4+a_2\delta ^2a_0.$$
(33)
Considering the same ratio as before we obtain

$$\frac{S}{2\pi RE}=\delta \frac{6a_6+4a_4\delta ^2+2a_2\delta ^4}{5a_6+3a_4\delta ^2+a_2\delta ^4a_0\delta ^6}.$$
(34)
The coefficients are related through

$$5a_63a_4+a_2+a_0=0,$$
(35)
and we have $`a_6,a_2>0`$, $`a_4,a_0<0`$ . The denominator can be factorized into

$$5a_6+3a_4\delta ^2+a_2\delta ^4a_0\delta ^6=(1+\delta ^2)(5a_6+(a_2+a_0)\delta ^2a_0\delta ^4).$$
(36)
Using the explicit values $`a_6=1/5`$, $`a_4=5/3`$, $`a_2=19`$, $`a_0=25`$ we obtain

$$\frac{S}{2\pi ER}=\frac{2\delta }{1+\delta ^2}\frac{\frac{3}{5}\frac{10}{3}\delta ^2+19\delta ^4}{16\delta ^2+25\delta ^4}.$$
(37)
This is a well-behaved function of $`\delta `$, which has a maximum of $`0.824`$. We therefore conclude that

$$\frac{S}{2\pi ER}0.824,$$
(38)
which is less stringent than the Verlinde CFT bound (4).

### 2.2 General entropy bounds in CFTs from monotonicity properties

In this subsection we show that entropy bounds in CFTs at finite temperature arise naturally from the monotonicity property of a generalized $`C`$-function . On general grounds, the free energy of a $`D`$-dimensional statistical system that can be described in its continuum limit by a renormalized field theory  can be written as

$$F(T,V,g_R)=E_0(V,g_R)T^D𝒞(T,V,g_R),$$
(39)
where $`V`$ is the total volume, $`g_R`$ denote collectively a set of renormalized couplings and $`E_0(V,g_R)`$ is the zero temperature energy of the system. For two-dimensional systems, the function $`𝒞(T,V,g_R)`$ is proportional to Zamolodchikov’s $`C`$-function  and for unitary quantum field theories it is a monotonically decreasing function along the RG-flow from the UV to the IR. For systems at finite temperature, however, one might also consider a change in the temperature at some fixed values of the coupling constants. Then, the question arising is how the above generalized $`C`$-function behaves in such a case. In a temperature interval where no phase transitions occur, a natural assumption is that the generalized $`C`$-function above behaves monotonically under temperature changes. For example, the $`C`$-function defined in (39) is proportional to the quantity used in  as a measure of the massless degrees of freedom coupled at a fixed point. In that case the IR and UV fixed points were taken, respectively, to be the $`T0`$ and $`T\mathrm{}`$ limits of (39). One then expects that the $`C`$-function above describes the process of thermal excitation of more and more degrees of freedom as the temperature is raised, in which case it seems natural to assume that

$$T\frac{}{T}𝒞(T)0.$$
(40)
Such a simple picture is consistent with the fact that the free energy density is minus the pressure.

The monotonicity property (40) leads to a general bound for the ratio of the entropy to the total energy of the above statistical system. From (39) we obtain after some simple algebra

$`S`$ $`=`$ $`T^{D1}\left[D𝒞+T{\displaystyle \frac{𝒞}{T}}\right],`$ (41)
$`EE_0`$ $`=`$ $`T^D\left[(D1)𝒞+T{\displaystyle \frac{𝒞}{T}}\right],`$ (42)
$`T{\displaystyle \frac{𝒞}{T}}`$ $`=`$ $`T^D\left[D(EE_0)(D1)TS\right].`$ (43)
From (41) and (42) we see that our definition of $`𝒞`$ is consistent with the third law of thermodynamics which requires that $`lim_{T0}S=0`$. We then easily see from (43) that the monotonicity property (40) leads to the bound

$$\frac{S}{2\pi R(EE_0)}\frac{D}{D1}\delta ,$$
(44)
with the same $`\delta =(2\pi RT)^1`$ as in the previous subsection. As it was discussed in , the bound (44) implies that the number of states with energy between $`E(T)`$ and $`E(T+\mathrm{\Delta }T)`$ in the underlying system is bounded from above. Such a property does not follow from the basic laws of thermodynamics.

The bound (44) also makes no reference to the specific properties of the underlying thermal CFT. For additional information one has to deal directly with a particular CFT model, such as the free field theories of subsection 2.1 or the strongly coupled CFTs of subsection 3.1. Nevertheless, comparing (2) and (43) we see that for systems with zero ground state energy (such as supersymmetric systems, cf. e. g. ), one has

$$T\frac{𝒞}{T}=T^DE_C.$$
(45)
Formula (45) relates the derivative of the generalized $`C`$-function to the sub-extensive part of the total energy and gives useful physical insight for the latter. For example, the property $`E_C0`$ which was required in  to give meaning to the Verlinde formula (3) is now equivalent to (40). Furthermore, the fact that $`E_C<0`$ for the massless free boson in $`D=4`$  can be attributed, by virtue of (45), to the temperature instability of the vacuum of that particular theory in which case we should not expect the analysis leading to formula (3) to be valid.

## 3 Entropy bounds in CFTs with AdS duals

### 3.1 General results

In this section we turn our attention to strongly coupled CFTs in $`D`$-dimensions, possessing AdS duals. The thermodynamics of such theories follows quite generally from the thermodynamics of $`(D+1)`$-dimensional AdS black holes, through holography. We consider the rotating Kerr-AdS (KAdS) black hole in $`(D+1)`$-dimensions given by 888For simplicity we restrict ourselves to the case of only one rotation parameter.

$`ds^2`$ $`=`$ $`{\displaystyle \frac{\mathrm{\Delta }_r}{\rho ^2}}[dt{\displaystyle \frac{a}{\mathrm{\Xi }}}\mathrm{sin}^2\theta d\varphi ]^2+{\displaystyle \frac{\rho ^2}{\mathrm{\Delta }_r}}dr^2+{\displaystyle \frac{\rho ^2}{\mathrm{\Delta }_\theta }}d\theta ^2`$ (46)
$`+{\displaystyle \frac{\mathrm{\Delta }_\theta \mathrm{sin}^2\theta }{\rho ^2}}[adt{\displaystyle \frac{r^2+a^2}{\mathrm{\Xi }}}d\varphi ]^2+r^2\mathrm{cos}^2\theta d\mathrm{\Omega }_{D3}^2,`$
where $`d\mathrm{\Omega }_{D3}^2`$ denotes the standard metric on the unit $`S^{D3}`$ and

$`\mathrm{\Delta }_r`$ $`=`$ $`(r^2+a^2)\left(1+{\displaystyle \frac{r^2}{R^2}}\right)2Mr^{4D},`$
$`\mathrm{\Delta }_\theta `$ $`=`$ $`1{\displaystyle \frac{a^2}{R^2}}\mathrm{cos}^2\theta ,`$ (47)
$`\mathrm{\Xi }`$ $`=`$ $`1{\displaystyle \frac{a^2}{R^2}},`$
$`\rho ^2`$ $`=`$ $`r^2+a^2\mathrm{cos}^2\theta .`$ (48)
The inverse temperature, free energy, entropy, energy and angular momentum read

$`\beta `$ $`=`$ $`{\displaystyle \frac{4\pi (r_+^2+a^2)}{(D2)\left(1+\frac{a^2}{R^2}\right)r_++\frac{Dr_+^3}{R^2}+\frac{(D4)a^2}{r_+}}},`$ (49)
$`F`$ $`=`$ $`{\displaystyle \frac{V_{D1}}{16\pi G_{D+1}\mathrm{\Xi }}}r_+^{D4}(r_+^2+a^2)\left({\displaystyle \frac{r_+^2}{R^2}}1\right),`$ (50)
$`S`$ $`=`$ $`{\displaystyle \frac{V_{D1}}{4G_{D+1}\mathrm{\Xi }}}r_+^{D3}(r_+^2+a^2),`$ (51)
$`E`$ $`=`$ $`{\displaystyle \frac{(D1)V_{D1}}{16\pi G_{D+1}\mathrm{\Xi }}}r_+^{D4}(r_+^2+a^2)\left({\displaystyle \frac{r_+^2}{R^2}}+1\right),`$ (52)
$`J`$ $`=`$ $`{\displaystyle \frac{aV_{D1}}{8\pi G_{D+1}\mathrm{\Xi }^2}}r_+^{D4}(r_+^2+a^2)\left({\displaystyle \frac{r_+^2}{R^2}}+1\right),`$ (53)
where $`G_{D+1}`$ is Newton’s constant, $`V_{D1}`$ denotes the volume of the unit $`S^{D1}`$, $`r_+`$ (the horizon radial coordinate) is the largest root of $`\mathrm{\Delta }_r=0`$, and the rotation parameter $`a`$ is restricted to the range $`0a<R`$. According to the AdS/CFT duality conjecture , the above thermodynamical quantities are associated to a strongly coupled $`D`$-dimensional CFT residing on the conformal boundary of the spacetime (46), i. e. on a rotating Einstein universe.

Defining $`\mathrm{\Delta }=R/r_+`$, and the Bekenstein entropy $`S_B=2\pi ER/(D1)`$, we obtain from (51) and (52)

$$\frac{S}{S_B}=\frac{2\mathrm{\Delta }}{1+\mathrm{\Delta }^2}1.$$
(54)
The Bekenstein bound is saturated for $`\mathrm{\Delta }=1`$, i. e. at the Hawking-Page transition point , where the free energy becomes zero. We further note that we can write

$$2ER=\frac{D1}{2\pi }S\frac{R}{r_+}[\mathrm{\Delta }^2+1],$$
(55)
which, for arbitrary $`D`$, is exactly the behavior of a two-dimensional CFT (17) with characteristic scale $`R`$, temperature $`\stackrel{~}{T}=1/(2\pi R\mathrm{\Delta })=r_+/(2\pi R^2)`$, and central charge proportional to $`SR/r_+`$. This resemblance motivates us to define the Casimir energy as the sub-extensive part of (55), i. e.

$$E_C=\frac{(D1)}{2\pi }\frac{S}{r_+}=\frac{D1}{2\pi }\frac{V_{D1}}{4G_{D+1}\mathrm{\Xi }}r_+^{D4}(r_+^2+a^2).$$
(56)
Note that in the non-rotating case $`a=0`$, (56) coincides with the expression 999The expressions in  are related to ours by $`L=R^2/r_+`$ and $`\frac{c}{12}\frac{V}{R^{2D2}}=\frac{V_{D1}}{4G_{D+1}}`$. given in .

One now easily verifies that the quantities (51), (52) and (56) satisfy exactly the Verlinde formula (3). We can also define the ”Casimir entropy”  by

$$S_C=\frac{2\pi }{D1}E_CR=S\frac{R}{r_+},$$
(57)
which allows to write the free energy as

$$FR=\frac{S_C}{4\pi }[\mathrm{\Delta }^21].$$
(58)
Comparing (58) with the corresponding relation of a two-dimensional bosonic CFT (16), we see that the Casimir entropy $`S_C`$ is essentially proportional to the central charge , or equivalently to the number of degrees of freedom coupled at the critical point.

Within such an interpretation for $`S_C`$ we can now see that the temperature $`\stackrel{~}{T}=r_+/(2\pi R^2)`$ makes thermodynamic sense as a temperature of a two-dimensional system. Considering for simplicity the case when $`a=0`$ and constant volume, the second law of black hole mechanics reads

$$dE(S,N)=TdS+\mu dN,$$
(59)
where by virtue of (57) and (51) we defined the number of degrees of freedom (generalized central charge) as

$$N=\frac{V_{D1}R^{D1}}{16\pi G_{D+1}}=\frac{S_C}{4\pi }\left(\frac{R}{r_+}\right)^{D2},$$
(60)
and $`\mu `$ is the chemical potential. After some algebra, we find

$$\mu =\left(\frac{r_+}{R}\right)^{D2}\left(\frac{r_+^2}{R^2}1\right)\frac{1}{R}.$$
(61)
The free energy (58) can then be written simply as

$$F=\mu N.$$
(62)
Furthermore, for $`S_C=`$ const., we have

$$d\stackrel{~}{E}=\stackrel{~}{T}dS,$$
(63)
where

$$\stackrel{~}{E}=E\frac{1}{D1},\stackrel{~}{T}=\frac{1}{D1}(T+\mu \frac{dN}{dS})=\frac{r_+}{2\pi R^2}.$$
(64)
Notice that $`\stackrel{~}{E}=E`$ and $`\stackrel{~}{T}=T`$ for $`D=2`$, as expected.

Remarkably enough, these results generalize to the $`a0`$ case. Even with the addition of one more potential and the attendant generalization of the second law of black hole mechanics to

$$dE=TdS+\mu dN+\mathrm{\Omega }dJ,$$
(65)
the condition $`dS_C=0`$ still describes a two-dimensional system.

Finally, as in  we define the ”Bekenstein-Hawking energy” $`E_{BH}`$ as the energy for which the black hole entropy $`S`$ (51) and the Bekenstein entropy $`S_B`$ are equal, $`2\pi E_{BH}R/(D1)=S`$, yielding

$$E_{BH}=E_C\frac{r_+}{R}.$$
(66)
One checks that $`E_{BH}E`$. Furthermore, because we are above the Hawking-Page transition point, we have $`r_+R`$, and therefore

$$E_CE_{BH}E,S_CSS_B,$$
(67)
where equality holds when the HP phase transition is reached. As the entropy $`S`$ is a monotonically increasing function of $`E_C`$ (or, equivalently, of $`r_+`$), the maximum entropy is reached when $`E_C=E_{BH}`$, i. e. at the HP phase transition $`r_+=R`$. It is quite interesting to observe that at this point the central charge $`c/12=S_C/(2\pi )`$ takes e. g. for $`D=4`$, $`𝒩=4`$ $`U(N)`$ SYM theory the value101010Here we used the AdS/CFT dictionary $`N^2=\frac{\pi R^3}{2G_5}`$. $`c=6N^2`$. This is exactly the central charge of a two-dimensional free CFT containing the $`6N^2`$ scalars of $`D=4`$, $`𝒩=4`$ SYM.

### 3.2 Scaling form for the free energy and entropy of CFTs with AdS duals

The results of the previous subsection suggest a simple scaling form for the free energy of strongly coupled $`D`$-dimensional CFTs at finite temperature. One motivation comes from expression (49), for $`a=0`$, which takes the form111111We keep only the positive root, the negative one being related to a branch of unstable black holes.

$$r_+(T,R)=R\frac{2\pi RT}{D}\left[1+\sqrt{1\frac{D(D2)}{(2\pi RT)^2}}\right],$$
(68)
that resembles the finite-size scaling of the correlation length - here $`r_+(T,R)`$ \- in a system with finite size $`R`$ at temperature $`T`$ . For such a system, the relation $`r_+(T,R)=R`$ defines the rounding temperature  which is an approximation to the true critical temperature. From the above, we see that the Hawking-Page temperature $`T_{HP}=(D1)/2\pi R`$  coincides with the rounding temperature of the finite-size system.

Interpreting $`r_+(T,R)`$ as the correlation length of a system with finite size $`R`$ at temperature $`T`$ makes all thermodynamical relations derived in the previous subsection similar to finite-size scaling. In particular, the basic assumption of finite-size scaling (see e.g. ), that there exists only one length scale in the theory is consistent with the fact that the dimensionless quantities $`ER`$, $`S`$ and $`FR`$ in (55), (51) and (58) are all given in terms of the ratio $`\mathrm{\Delta }=R/r_+`$. In this sense, one could have started by postulating certain simple scaling relations for the above thermodynamical quantities which would then describe an underlying system of finite extent $`R`$ at temperature $`T`$. As an example, in $`D`$ dimensions we could have postulated the following scaling relation for the dimensionless quantity $`FR`$, in the regime $`r_+>R`$,

$$FR=G^{(2)}(\mathrm{\Delta })\mathrm{\Delta }^{2D},$$
(69)
where the function $`G^{(2)}(x)`$ is given by

$$G^{(2)}(x)=K(1x^2),$$
(70)
and $`24K`$ is a constant playing the role of a generalized central charge. Clearly, (69) is a simple generalization of the two-dimensional relation (16). Such a relation implies that in the finite-size scaling regime where $`R,r_+\mathrm{}`$ but $`\mathrm{\Delta }`$ finite, the free energy density $`f`$ (free energy per unit spatial volume ) behaves as $`fR^D`$, as it should for a $`D`$-dimensional system with finite size $`R`$.

Next we have to make sure that (69) satisfies the basic thermodynamical equation at constant volume

$$\frac{}{T}F=\frac{\mathrm{\Delta }}{T}\frac{}{\mathrm{\Delta }}F=S.$$
(71)
Requiring then a simple scaling form for $`S`$ would give a differential equation that could determine $`\mathrm{\Delta }`$ and consequently $`r_+(T,R)`$. We can check this in $`D=2`$ where $`K`$ in (69) is proportional to the central charge of the theory. In this case we know that (see e.g. (17))

$$S=S^{(2)}4\pi K\mathrm{\Delta }^1.$$
(72)
Plugging this into (71) we easily obtain $`\mathrm{\Delta }=(2\pi RT)^1`$ which is the standard two-dimensional result.

The two-dimensional relation (72) has a nice physical content away from the critical point as it relates the two-dimensional $`C`$-function, which corresponds to the off-critical value of $`24K`$, to the entropy of the system. Had we wanted to keep such a physical picture in higher dimensions, we should require a form for the entropy similar to (72). To this end we suggest that in the $`D`$-dimensional system the following generalization of the two-dimensional result (72) should hold

$$S=S^{(2)}\mathrm{\Delta }^{2D}.$$
(73)
Plugging this into (71) we obtain

$$\left[(D2)D\frac{1}{\mathrm{\Delta }^2}\right]\frac{\mathrm{\Delta }}{T}=4\pi R,$$
(74)
whose solution finally yields

$$Dr_+^24\pi R^2Tr_++R^2(D2)=0.$$
(75)
The above is exactly the relation (49) (for $`a=0`$), coming from the study of AdS black hole thermodynamics.

## 4 Conclusions and Discussion

In the present work we studied the entropy bounds in $`D`$-dimensional CFTs both at the free field theory level as well as at strong coupling. Using the results of  we showed that the ratio of the entropy to the total energy is bounded for the free field realizations of $`𝒩=4`$ $`U(N)`$ SYM theory in $`D=4`$ and the $`(2,0)`$ tensor multiplet in $`D=6`$. We pointed out that general bounds for the entropy to energy ratio in CFTs at finite temperature follow from the requirement of monotonicity of a generalized $`C`$-function with respect to temperature changes. We showed that such a generalized $`C`$-function is related to the sub-extensive part of the total energy. Then we showed that for CFTs in a rotating Einstein universe possessing AdS duals, the Verlinde entropy formula (3) is still valid. We further suggested that if we interpret the horizon distance $`r_+(T,R)`$ as a correlation length, formulas (49)-(53) (for $`a=0`$) describe the thermodynamics of a $`D`$-dimensional statistical system of finite extent $`R`$ at finite temperature. The rounding temperature, which is an approximation to the critical temperature, of such a system is given by the Hawking-Page transition temperature. Assuming then simple scaling forms for the free energy and the entropy of the system, yields an explicit formula for the correlation length $`r_+(T,R)`$ which coincides with the result (49) coming from the thermodynamics of AdS black holes.

Let us briefly mention one implication of our results for cosmology. As in in Ref. , consider a radiation dominated closed Friedman-Robertson-Walker (FRW) universe. The FRW metric takes the form

$$ds^2=d\tau ^2+^2(\tau )d\mathrm{\Omega }_{D1}^2,$$
(76)
where $`(\tau )`$ represents the radius of the universe at a given time $`\tau `$. Note that the metric (76) is conformally equivalent to

$$d\stackrel{~}{s}^2=dt^2+R^2d\mathrm{\Omega }_{D1}^2,$$
(77)
where $`dt=Rd\tau /(\tau )`$. If the radiation is described by a CFT, one can equally well use (77) instead of (76). If, in addition, this CFT admits an AdS dual, it can be described by a Schwarzschild-AdS black hole at some temperature $`T`$, because (77) is precisely the metric on the conformal boundary of (46) for $`a=0`$121212In what follows, we shall only consider the static case $`a=0`$.. The observations made by Verlinde  concerning entropy, energy and temperature bounds in a radiation dominated universe then fit nicely into this AdS black hole description. In particular, the universe is weakly (strongly) self-gravitating if $`H1`$ ($`H1`$), where $`H=\dot{}/`$ denotes the Hubble constant, and the dot refers to differentiation with respect to $`\tau `$. One has $`H=1`$ iff the Bekenstein-Hawking entropy $`S`$ equals the Bekenstein entropy $`S_B`$. We saw above that this happens precisely at the HP transition point $`r_+=R`$, so the borderline between the weakly and strongly self-gravitating regime is the Hawking-Page phase transition temperature $`T_{HP}=(D1)/2\pi R`$. This identification makes indeed sense, because below $`T_{HP}`$ (weakly gravitating) one has AdS space filled with thermal radiation which collapses above $`T_{HP}`$ ($`r_+R`$, strongly gravitating) to form a black hole. Furthermore, in  a limiting temperature was found for the early universe,

$$TT_H=\frac{\dot{H}}{2\pi H}\text{for}H1.$$
(78)
We conclude therefore that Verlinde’s limiting temperature $`T_H`$ corresponds to the temperature $`T_{HP}`$ where the HP phase transition takes place.

Concerning further developments of our ideas, it might be interesting to study our generalized central charge defined in (60). We discussed in the text that this quantity intriguingly resembles a standard two-dimensional central charge. Such an interpretation leads to the conjecture that there might exist a two-dimensional CFT model whose dynamics in the presence of irrelevant operators, as follows from (69) and (73), underlies the dynamics of the $`D`$-dimensional CFTs possessing AdS duals. Such a conjecture might explain the fact that the latter theories share unexpectedly many of the properties of two-dimensional CFTs .

It would also be interesting to understand what happens if the sub-extensive part of the total energy becomes negative. This is e. g. the case for hyperbolic AdS black holes. As $`E_C`$ corresponds somehow to a central charge, this would indicate that the underlying CFT is non-unitary or that the theory has a thermally unstable ground state.

Another point that needs to be understood is the underlying model which produces the simple scaling relations for the free energy and the entropy described in section 3.2. This might be of some interest as the scaling relations (69) and (73) seem to have a wide application range. Different choices of the scaling function (70) would lead to formulas for the correlation length $`r_+(R,T)`$ different from (75). As an example, one could try to generalize relations (13) and (14) for the free energy and entropy of the massless free boson in $`D=4`$. A possible generalization in the spirit of (69) and (73) would give the free energy and entropy of a $`D`$-dimensional CFT as

$$FR=𝒦(1+\frac{1}{3}\mathrm{\Delta }^4)\mathrm{\Delta }^{4D},S=\frac{8\pi 𝒦}{3}\mathrm{\Delta }^{1D}.$$
(79)
Then, one can show that imposition of the basic thermodynamical relation (71) leads to a differential equation whose solution yields

$$Dr_+^424\pi R^2Tr_+^3(D4)R^4=0.$$
(80)
It remains to be seen if $`r_+`$ in (80) corresponds to the horizon distance of some new kind of black holes in dimensions $`D+15`$.

## Acknowledgments

D. K. is partially supported by MURST and by the European Commission RTN program HPRN-CT-2000-00131, in which he is associated to the University of Torino. A. C. P. is supported by the European Commission RTN program HPRN-CT-2000-00131, in which he is associated to the University of Torino. G. S. is supported by the US Department of Energy under grant DE–FG05–91ER40627.