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# Level Correlations for Metal-Insulator Transition

## Abstract

We study the level-statistics of a disordered system undergoing the Anderson type metal-insulator transition. The disordered Hamiltonian is a sparse random matrix in the site representation and the statistics is obtained by taking an ensemble of such matrices. It is shown that the transition of levels due to change of various parameters e.g. disorder, system size, hopping rate can be mapped to the perturbation driven evolution of the eigenvalues of an ensemble subjected to Wigner-Dyson type perturbation with an initial state given by a Poisson ensemble; the mapping is then used to obtain desired level-correlations.

. The degree of disorder and dimensionality of a disordered system plays a significant role in the metal-insulator (MI) transition . The level statistics during the transition is governed by a parameter which is a function of both, disorder as well as dimensionality . The purpose of this paper is to identify the parameter and study the effect of its variation on the spectral fluctuations.

The statistical behaviour of the levels of a disordered Hamiltonian depends on their number $`r`$ within the energy ranges of interest and the dimensionless conductance $`g`$. The parameter $`g`$ is the ratio of two energy scales, namely, Thouless energy $`E_c`$ and mean level spacing $`\mathrm{\Delta }`$. The energy scale $`E_c=\overline{h}D/L^2`$, with $`D`$ as diffusion coefficient and $`L`$ system size, corresponds to ergodic time-scales (ergodic classical limit) above which the wavefunction has fully diffused in the entire volume $`L_d`$ of the system and therefore does not feel the space dimensionality $`d`$. The eigenfunctions associated with levels within energy ranges smaller than $`E_c`$ are extended structureless objects leaving no signature on the level correlations. The number $`r<g`$, therefore, results in a universality of level correlations which can be well-modeled by the invariant ensembles of random matrix theory (RMT) . For $`r>g`$, the time scales associated with the dynamics are such that the wavefunction is not yet fully diffused in the whole volume. The eigenfunctions in the corresponding energy-range are localized, either partially or fully depending on the dimensionality, and their spatial correlations can significantly affect the level correlations.

The metallic phase of a disordered system corresponds to $`g\mathrm{}`$ in the thermodynamic limit $`L\mathrm{}`$. The states, therefore, in any large but finite interval are always extended with a Wigner-Dyson (WD) level-statistics, characterstic of strong level-repulsion . In the insulator phase $`g0`$ in the thermodynamic limit, implying no overlap between eigenfunctions. The corresponding level statistics can be modeled by the statistics of independent random numbers, that is, Poisson statistics. A change in the degree of disorder results in the variation of $`g`$ (for fixed $`r`$) which can induce a transformation of extended states into localized states thereby causing a transition of spectral fluctuations. However the MI transition is very sensitive to the dimensions of the system. For $`d=1,2`$ and, in thermodynamic limit, the system always remains an insulator even for very weak disorder. For $`d>2`$, the increase of disorder results in decreasing $`g`$, leading to an extended to localized state transition at a critical value of disorder. In the region near the critical point of the transition, known as Anderson transition, the eigenstates are neither localized nor extended but form self-similar multifractal structures with strong fluctuations at all length scales. This results in a new type of universal level-statistics, known as critical spectral statistics (CSS), which is neither Poissonian nor Wigner-Dyson but is a hybrid of both . For finite system size also, a crossover from Poisson to WD statistics can be seen among levels as a function of the parameter $`\zeta /L`$ with $`\zeta `$ as the correlation length. However the detailed analytical information about various level correlations in the critical regime for inifinte systems as well as for the intermediate stages, during transition in finite systems, is still missing. Our study attempts to bridge this gap.

The level statistics for various transition stages is significantly affected by the nature of the localization of the eigenfunctions and can suitably be modeled by an ensemble containing eigenvalue-eigenfunction correlations (therefore basis-dependent). Recently a new technique has been developed to deal with such cases where the eigenvalue distribution for an ensemble, non-invariant under a change of basis, is mapped to the one for an ensemble invariant under change of basis and subjected to a random perturbation . The mapping is achieved by identifying a basis-dependent parameter in the former to the perturbation (e.g symmetry-breaking) parameter in the latter. The distribution for the invariant case can subsequently be mapped to the non-stationary states of the particles governed by Calogero-Sutherland-Moser (CSM) Hamiltonian . The known particle correlations can therefore be used to determine level-correlations of the non-invariant ensembles. The present study uses the technique to analyze the spectral properties of the levels undergoing MI transition by taking an ensemble of Anderson Hamiltonains in the site representation. As expected, the basis dependent parameter, governing the transition in this case, is a function of disorder, dimensionality and hopping rate and is related to $`g`$.

The Anderson model for a disordered system is described by a d-dimensional disordered lattice, of size $`L`$, with a Hamiltonian $`H=_nϵ_na_n^+a_n+_{nm}t(a_n^+a_m+a_na_m^+)`$ in tight-binding approximation . Here $`a_n^+`$ and $`a_n`$ are the creation and annihilation operators of an electron at a site $`n`$ in a lattice and $`m`$ refers to the nearest neighbors of the site $`n`$. The site energies $`ϵ_n`$, measured in units of the overlap integral between adjacent sites correspond to the random potential. The hopping is generally assumed to connect only the $`z`$ nearest-neighbors with amplitude $`t`$ so that the electron kinetic energy spread or bandwidth is $`zt`$. In the configration space representation the Hamiltonian $`H`$ turns out to be a sparse matrix of size $`N=L^d`$ with diagonal matrix elements as the site-energies $`ϵ_i`$. The level-statistics can therefore be studied by analyzing the properties of an ensemble of (i) sparse real symmetric matrics in presence of a time-reversal symmetry and (ii) sparse complex Hermitian matrice in absence of a time-reversal symmetry.

We first consider the case of MI transition brought about by decreasing the diagonal disorder. In this case, site-energies $`ϵ_i`$ are taken to be independent random variables with probability-density $`p(ϵ_i)`$. In the original Anderson model  $`p(ϵ)`$ was taken to be a constant $`W^1`$ between $`W/2`$ to $`W/2`$. Various physical arguments and approximations used in this case led to conclusion that all the states are localized for $`W>4Kt\mathrm{ln}(\frac{W}{2t})`$ with $`K`$ as a function of $`z`$ and $`d`$. However, as well-known now, MI transition does not depend on the nature of $`p(ϵ)`$ and latter can also be chosen as Gaussian; the type of $`p(ϵ)`$ affects only the critical point of the transition . The ensemble measure $`\rho (H)`$, for any intermediate state of MI transition brought about by diagonal disorder, can therefore be described by $`\rho (H,y,b)\mathrm{exp}(_{s=1}^2_k\alpha _{kk;s}(H_{kk;s}b_{kk;s})^2)_{kl;s=1,2}\delta (H_{kl;s}b_{kl;s})`$ with subscript $`\mathrm{"}s\mathrm{"}`$ referring to real and imaginary parts and the Kronecker delta function implying the non-randomness of off-diagonal matrix element ($`H_{kl}=b_{kl;1}+ib_{kl;2}`$). However $`\rho (H)`$ can be expressed in a more general form:

$`\rho (H,y,b)=C\mathrm{exp}({\displaystyle \underset{s=1}{\overset{2}{}}}{\displaystyle \underset{kl}{}}\alpha _{kl;s}(H_{kl;s}b_{kl;s})^2)`$ (1)
with $`C=_{kl}_{s=1}^2\sqrt{\frac{\alpha _{kl;s}}{\pi }}`$ as the normalization constant, $`y`$ as the set of the coefficients $`y_{kl;s}=\alpha _{kl;s}g_{kl}=\frac{g_{kl}}{2<H_{kl;s}^2>}`$ and $`b`$ as the set of all $`b_{kl;s}`$ with $`g_{kl}=1+\delta _{kl}`$. As obvious, in limit $`\alpha _{kl;1},\alpha _{kl;2}\mathrm{}`$, eq.(1) corresponds to the non-random nature of the off-diagonal part of $`H`$. However note, for later reference, that a same mean value for all the matrix elements, that is $`b_{kl;s}=ϵ`$ for all $`k,l`$ (irrespective of $`\alpha _{kl}`$ values) implies just a shift of the origin in the matrix space and does not affect the eigenvalue distribution.

The MI transition is brought about by a competitive variation of the disorder and hopping rate which can be mimicked by a change of the distribution parameters of $`\rho (H)`$. The changed eigenvalue distribution as a result can be obtained by integrating $`\rho (H)`$ over associated eigenvector space. Let $`P(\mu ,y,b)`$ be the probability of finding eigenvalues $`\lambda _i`$ of $`H`$ between $`\mu _i`$ and $`\mu _i+\mathrm{d}\mu _i`$ at a given $`y`$ and $`b`$, it can be expressed as $`P(\mu ,y,b)=_{i=1}^N\delta (\mu _i\lambda _i)\rho (H,y,b)\mathrm{d}H`$. As discussed in ref., a particular combination of the evolution of $`P`$ with respect to various distribution parameters, namely, $`DP2_s_{kl}y_{kl;s}(\gamma y_{kl;s})\frac{P}{y_{kl;s}}\gamma _s_{kl}b_{kl;s}\frac{P}{b_{kl;s}}`$, with $`\gamma `$ as an arbitrary parameter, results in the diffusion of eigenvalues with a finite drift due to their mutual repulsion.

$`DP`$ $`=`$ $`{\displaystyle \underset{n}{}}{\displaystyle \frac{}{\mu _n}}\left[{\displaystyle \frac{}{\mu _n}}+{\displaystyle \underset{mn}{}}{\displaystyle \frac{\beta }{\mu _m\mu _n}}+\gamma \mu _n\right]P`$ (2)
with $`\beta `$ depending on the symmetry class of the ensemble ($`\beta =1`$ for real symmetric matrices and $`\beta =2`$ for complex Hermitian ones). The multi-parametric evolution of $`P`$ can further be reduced in terms of the evolution with respect to a single parameter $`Y`$, that is, $`DP=\frac{P}{Y}`$ where $`Y`$ is a function of various $`y_{kl;s}`$ and $`b_{kl;s}`$ ,

$`Y={\displaystyle \frac{1}{2N^2}}{\displaystyle \underset{kl}{}}{\displaystyle \underset{s=1}{\overset{2}{}}}\left[{\displaystyle \frac{1}{2}}\mathrm{ln}{\displaystyle \frac{y_{kl;s}}{|y_{kl;s}\gamma |}}{\displaystyle \frac{1}{\gamma }}\mathrm{ln}|b_{kl;s}|\right]+C`$ (3)
and can therefore be referred as the ’complexity parameter’. Here $`C`$ is an arbitrary constant. The eq.(2) can now be rewritten as follows,

$`{\displaystyle \frac{P}{Y}}`$ $`=`$ $`{\displaystyle \underset{n}{}}{\displaystyle \frac{}{\mu _n}}\left[{\displaystyle \frac{}{\mu _n}}+{\displaystyle \underset{mn}{}}{\displaystyle \frac{\beta }{\mu _m\mu _n}}+\gamma \mu _n\right]P`$ (4)
For $`y_{kl;s}\gamma `$ and $`b_{kl;s}ϵ`$ (for almost all $`k,l`$), $`DP0`$ and the evolution reaches the steady state given by a WD distribution $`P(\mu )=_{i<j}|\mu _i\mu _j|^\beta \mathrm{e}^{\frac{\gamma }{2}_k\mu _k^2}`$. (Note, in this limit, $`\rho (H)\mathrm{e}^{\gamma \mathrm{Tr}H^2ϵ\mathrm{Tr}H}`$ which indeed has a WD distribution and therefore agrees with the solution of eq.(4) in limit $`DP0`$). The eq.(4) is similar to the equation governing a perturbation driven transition of the eigenvalues, of a Hamiltonian $`H=H_0+\tau V`$, between various universality classes of WD ensembles. Here $`H_0`$ is an initial ensemble with perturbation $`V`$ causing a transition to another (or same) universality class. The transition to equilibrium, with perturbation strength $`\tau `$ as the evolution parameter, is rapid, discontinuous for infinite dimensions of matrices (analogous to Anderson transition). But for small-$`\tau `$ and large $`N`$, a smooth transition can be seen in terms of a rescaled parameter $`\mathrm{\Lambda }`$ which measures locally the mean-square perturbation matrix element in units of the average level spacing . The intermediate states of this transition have been well-studied in past and many results for their spectral fluctuations are already known . By replacing the perturbation parameter by complexity parameter, these results can directly be used for the corresponding measures for the MI transition. Note this is eqivalent to say that if the initial Anderson Hamiltonian is described by $`H_0`$, the changing complexity (the combined effect of changing disorder and hopping rate) can be treated as a perturbation $`V`$ of strength $`Y`$, taken from WD ensemble, with Hamiltonian $`H`$ of the system represented by $`H=H_0+YV`$.

The $`n^{\mathrm{th}}`$ order level density correlation $`R_n`$ is defined as $`R_n=<\nu (\mu _1,Y)..\nu (\mu _n,Y)>`$ with $`\nu (\mu ,Y)=N^1_i\delta (\mu \mu _i)`$ as the density of eigenvalues and $`<..>`$ implying the ensemble average. The $`R_n`$ can also be expressed in terms of $`P`$: $`R_n=\frac{N!}{(Nn)!}P(\mu ,Y)\mathrm{d}\mu _{n+1}..\mathrm{d}\mu _N`$. A solution of eq.(4), averaged over initial conditions, can therefore be used to obtain various correlations for a given set of distribution parameters. In practice, however, the involved integrals could only be solved for the cases when $`H`$ is complex Hermitian in nature . a direct integration of F-P equation (4) leads to the BBGKY hierarchic relations among the unfolded correlators $`R_n(r_1,..,r_n;\mathrm{\Lambda })=\mathrm{Lim}N\mathrm{};\frac{R_n(\mu _1,..,\mu _n;Y)}{R_1(\mu _1;Y)\mathrm{}R_1(\mu _n;Y)}`$ with $`r=^rR_1(\mu ;Y)dY`$ and $`\mathrm{\Lambda }=(YY_0)\gamma /\mathrm{\Delta }^2`$ ($`\mathrm{\Delta }`$ as the mean level spacing $`=R_1^1=(N<\nu >)^1`$) ,

$`{\displaystyle \frac{R_n}{\mathrm{\Lambda }}}`$ $`=`$ $`{\displaystyle \underset{j}{}}{\displaystyle \frac{^2R_n}{r_j^2}}\beta {\displaystyle \underset{jk}{}}{\displaystyle \frac{}{r_j}}\left({\displaystyle \frac{R_n}{r_jr_k}}\right)\beta {\displaystyle \underset{j}{}}{\displaystyle \frac{}{r_j}}{\displaystyle _{\mathrm{}}^{\mathrm{}}}{\displaystyle \frac{R_{n+1}}{r_jr_k}}`$ (5)
Here note a perturbation of strength $`\mathrm{\Lambda }`$ mixes levels in a spectrum span of $`\sqrt{\mathrm{\Lambda }}`$ only, due to level repulsion . This results in a sensitivity of the correlations within a given energy range $`r`$ to the ratio $`r/\sqrt{\mathrm{\Lambda }}`$. In the case of MI transition, therefore, $`\mathrm{\Lambda }`$ can be identified with $`g^2`$.

For $`n=2`$ and small values of $`r`$, the integral term in eq.(5) makes a negligible contribution thus leading to following approximated closed form equation for $`R_2`$

$`{\displaystyle \frac{R_2}{\mathrm{\Lambda }}}`$ $`=`$ $`2{\displaystyle \frac{^2R_2}{r^2}}2\beta {\displaystyle \frac{}{r}}{\displaystyle \frac{R_2}{r}}`$ (6)
Similarly for large-$`r`$ behaviour, $`R_2`$ can be obtained from the following relation

$`R_2(r,\mathrm{\Lambda })=R_2(r,\mathrm{})+2\beta \mathrm{\Lambda }{\displaystyle _{\mathrm{}}^{\mathrm{}}}ds{\displaystyle \frac{R_2(rs;0)R_2(rs;\mathrm{})}{s^2+4\pi ^2\beta ^2\mathrm{\Lambda }^2}}.`$ (7)
The hierarchic equation can then be used to obtain an approximate form of the higher order correlations. For example, the approximate information about $`R_3`$ can be extracted by a substitution of large and small $`r`$ behaviour of $`R_2`$ in eq.(5) with $`n=2`$.

For studies of the level-correlations during MI transition, the system can initially be considered in an insulator regime where all the eigenvectors become localized on individual sites of the lattice (strong disorder limit). This results in a diagonal form of the matrix $`H`$ with the eigenvalues independent from each other. The insulator limit can therefore be modeled by ensemble (1) with $`\alpha _{kl}\mathrm{}`$ for $`kl`$, $`\alpha _{kk}=\alpha _I`$ (for all $`k`$-values) and $`b_{kl}ϵ`$ (for all $`k,l`$), giving, $`Y_0=\frac{1}{4N}\mathrm{ln}\frac{2\alpha _0}{|2\alpha _0\gamma |}\frac{1}{\gamma }\mathrm{ln}ϵ+C`$. (Here the origin of the energy-axis is chosen at $`ϵ`$ so as to avoid the undefined nature of $`\mathrm{ln}b_{kl}`$ near $`b_{kl}0`$). The decrease of the diagonal disorder, that is, an increase of $`\alpha _{kk}`$ from $`\alpha _0`$ to some finite values (while $`\alpha _{kl}`$, $`kl`$, remains infinite throughout the transition) will ultimately lead to metal regime with fully delocalized wavefunctions. A change in the hopping rate of the connected sites from $`ϵ`$ to $`ϵ+t`$ ($`b_{kl}ϵ+t`$ for only those $`k,l`$ values which are connected, $`b_{kl}=ϵ`$ for others) will also affect the transition. As mentioned above, the eigenvalue distribution of $`H`$ in the metal regime can be well-modeled by the WD ensemble; let it be described by all $`\alpha _{kl}\alpha _M`$($`>\alpha _0`$). Thus for the study of transition in this case we can choose $`\gamma =2\alpha _M`$. For any intermediate state of the transition with hopping rate $`t`$ and disorder coefficient $`\alpha `$, the complexity parameter $`Y=\frac{1}{2N^2}\left[\frac{N}{2}\mathrm{ln}\frac{2\alpha }{|2\alpha \gamma |}\frac{K}{\gamma }\mathrm{ln}(t+ϵ)\frac{2N^2K}{\gamma }\mathrm{ln}ϵ\right]+C`$. Here $`K=\kappa N`$ is the total number of the sites connected by hopping and depends on the dimensionality $`d`$ of the system (as $`N=L^d`$). The transition parameter can now be given as follows, with the mean level spacing $`\mathrm{\Delta }=(<\nu >N)^1`$: $`\mathrm{\Lambda }=2\alpha _M(YY_0)/\mathrm{\Delta }^2=\alpha _M<\nu >^2Na(\alpha ,t)/2`$ with $`a(\alpha ,t)\left[\mathrm{ln}\frac{\alpha |\alpha _0\alpha _M|}{\alpha _0|\alpha \alpha _M|}\frac{\kappa }{\alpha _M}\mathrm{ln}\frac{t+ϵ}{ϵ}\right]`$. As obvious from the above, the transition is governed by relative values of the disorder and the hopping. Here $`\mathrm{\Lambda }0`$ leads to a fully localized regime which, corresponds to the condition $`a(\alpha ,t)<\frac{1}{N}.`$ Similarly the condition $`a(\alpha ,t)>\frac{1}{N}`$ corresponds to $`\mathrm{\Lambda }\mathrm{}`$ for large $`N`$ and therefore extended states. For $`a(\alpha ,t)=\frac{\mu }{N}`$ ($`\mu `$ as a $`N`$-independent function), $`\mathrm{\Lambda }=\alpha _M<\nu >^2\mu \mathrm{\Lambda }^{}`$ is independent of $`N`$ which therefore remains same for infinite systems ($`<\nu >`$ being independent of $`N`$). This $`\mathrm{\Lambda }`$-value corresponds to the critical point of the transition in infinite systems, the statistics being Poisson and WD below and above $`\mathrm{\Lambda }^{}`$, respectively. The condition for the critical region or mobility edge can therefore be given as $`\mathrm{ln}\frac{\alpha }{\alpha _0}+\frac{\alpha \alpha _0}{\alpha _M}\frac{\kappa }{\alpha _M}\mathrm{ln}(t+1)`$ (taking $`ϵ=1`$ without any loss of generality). As $`\frac{|\alpha \alpha _0|}{\alpha _M}<<1`$ even for large $`\alpha `$-values, the condition is always satisfied if $`\frac{\kappa }{\alpha _M}0`$. This explains the localization of all the states in infinitely long wires (or strictly 1-d systems where $`z`$ is very small) even for very weak disorder. With increasing dimensionality $`d`$, connectivity $`K`$ of the lattice and thereby the possibility of $`\mathrm{\Lambda }>>0`$ and the delocalized states increases. As reflected by its form, $`\mathrm{\Lambda }`$ also plays the role of the finite size scaling parameter. Note that the $`\mathrm{\Lambda }`$-dependence of various correlators indicates an interaction of levels different from that of Poisson or WD if $`\mathrm{\Lambda }`$ remains finite in limit $`N\mathrm{}`$. This implies the presence of a new type of universal statistics near the critical point $`\mathrm{\Lambda }^{}`$ of the transition. For finite systems, however, there is a continuous family of intermediate statistics between Poisson and WD, described by $`\mathrm{\Lambda }`$ and the symmetry of the Hamiltonian.

The fluctuation measures for various stages of the MI transition can be obtained from those of the perturbation driven Poisson $``$ WD ensemble transition, by replacing perturbation parameter by $`Y`$. The two level density correlator $`R_2(r;\mathrm{\Lambda })`$ for the Anderson transition in finite systems, in presence of a magnetic field, can therefore be given by the $`R_2`$ for Poisson $``$ GUE transition driven by the perturbation:

$`R_2(r;\mathrm{\Lambda })R_2(r;\mathrm{})={\displaystyle \frac{4}{\pi }}{\displaystyle _0^{\mathrm{}}}dx{\displaystyle _1^1}dz\mathrm{cos}(2\pi rx)\mathrm{exp}\left[8\pi ^2\mathrm{\Lambda }x(1+x+2z\sqrt{x})\right]\left({\displaystyle \frac{\sqrt{(1z^2)}(1+2z\sqrt{x})}{1+x+2z\sqrt{x}}}\right)`$ (8)
where $`R_2(r,\mathrm{})=1\frac{\mathrm{sin}^2(\pi r)}{\pi ^2r^2}`$ and $`R_2(r,0)=1`$ corresponding to metal and insulator regime respectively. A substitution of $`\mathrm{\Lambda }=\mathrm{\Lambda }^{}`$ in eq.(8) will thus give the two level correlation for critical regime of Anderson transition.

An important characterstic of CSS is the level compressibility $`\chi `$ which is basically a measure of the level repulsion; $`\chi =0`$ in the metallic phase and $`\chi =1`$ in the insulator phase and takes an intermediate value between $`0`$ and $`1`$ at the hybrid phase near the critical point. The eq.(4.15) of  can be used to obtain $`\chi (\mathrm{\Lambda })1_{\mathrm{}}^{\mathrm{}}Y_2(r;\mathrm{\Lambda })dr`$ with $`Y_2=1R_2`$, $`\chi (\mathrm{\Lambda })=1+_0^{\mathrm{}}du\frac{\mathrm{\Lambda }}{z}[I_1(z)\sqrt{8z/\pi }I_2(z)]\mathrm{exp}[(\mathrm{\Lambda }/2)u^2\pi \sqrt{\mathrm{\Lambda }/2}u]`$ with $`z=\sqrt{2\pi \mathrm{\Lambda }^2u^3}`$ and $`I_n`$ as the $`n^{\mathrm{th}}`$ Bessel function. (Note eq.(8) can not directly be used to calculate $`\chi `$ due to technical difficulties). It can be checked that $`\chi 1`$ for $`\mathrm{\Lambda }0`$ (insulator limit) and $`\chi 0`$ for $`\mathrm{\Lambda }\mathrm{}`$ (metal limit). As obvious from the smooth nature of the functional form of $`\chi `$, any non-zero finite $`\mathrm{\Lambda }`$-value will correspond to a value of $`\chi `$ intermediate between zero and one. The critical region will thus have a finite level compressibility different from both metal and insulator regimes and therefore multifractal nature of the eigenvectors .

The statistical measures for the Anderson transition in presence of a time-reversal symmetry can similarly be obtained by using their equivalence to those for the Poisson $``$ GOE transition. Although much information is not available about the latter (due to the technical difficulties in integrating over associated orthogonal space of eigenvectors) however some approximate results are known. For example, the $`R_2`$ for small $`r`$ can be obtained by solving the eq.(6) for $`\beta =1`$, $`R_2(r,\mathrm{\Lambda })(2r1)^{1/2}J_{1/3}\left((2r1)^{3/2}/3\mathrm{\Lambda }\right)\mathrm{e}^{r/2\mathrm{\Lambda }}`$ with $`J(z)`$ as the Bessel function. For $`r<<\sqrt{\mathrm{\Lambda }}`$, $`R_2r`$ implying level-repulsion of the same degree as for the delocalized regime; this is consistent with description of $`\mathrm{\Lambda }`$ as $`g^2`$. For large-$`r`$, $`R_2`$ can be obtained from eq.(7) by taking $`R_2(r;0)=1`$ (Poisson limit), $`\beta =1`$ and $`R_2(r,\mathrm{})=1\frac{\mathrm{sin}^2(\pi r)}{\pi ^2r^2}\left(_r^{\mathrm{}}dx\frac{\mathrm{sin}\pi x}{\pi x}\right)\left(\frac{\mathrm{d}}{\mathrm{d}r}\frac{\mathrm{sin}\pi r}{\pi r}\right)`$ (GOE limit); $`R_2(r,\mathrm{\Lambda })R_2(r,\mathrm{})+\frac{4\mathrm{\Lambda }}{r^2+4\pi ^2\beta ^2\mathrm{\Lambda }^2}`$ .

The exact formulation for the level compressibility $`\chi `$ for this case can not be obtained due to lack of the knowledge of $`R_2(r,\mathrm{\Lambda })`$ for entire energy-range. However the presence of a non-zero, non-unity compressibility can also be seen from the nearest-neighbour spacing distribution $`P(s)`$ for large $`s`$ values. This is because the compressibility of the spectrum is basically a reflection of the correlations of levels at large distances. For WD case, $`P(s)s\mathrm{e}^{\pi s^2/4}`$ decays as a Gaussian near the tail indicating no compressibility of levels. As for Poisson limit $`P(s)\mathrm{e}^s`$, the unity coefficient of $`s`$ in the exponent implies a very high degree of compressibility. An exponential tail of $`P(s)`$ with a non-unity coefficient will thus correspond to a a compressibility less than Poisson case; if $`P(s)\mathrm{e}^{ks}`$ for large $`s`$, $`\chi 1/2k`$. The $`P(s)`$ for MI transition can be given by using the one for the Poisson $``$ GOE transition , $`P(s,\mathrm{\Lambda })=\frac{su^2(\mathrm{\Lambda })}{\mathrm{\Lambda }}\mathrm{e}^{u^2(\mathrm{\Lambda })s^2/4\mathrm{\Lambda }^2}_0^{\mathrm{}}d\zeta \mathrm{e}^{\zeta ^22\zeta \mathrm{\Lambda }}I_0(s\zeta u(\mathrm{\Lambda })/\mathrm{\Lambda })`$ with $`u(\mathrm{\Lambda })=\sqrt{\pi }U(1/2,0,\mathrm{\Lambda }^2)`$, $`U`$ being Kummer function and $`I_0`$ Bessel function. Although this result is rigorous for $`2\times 2`$ matrix space but is proved reliable for systems with many levels. (The dominance of nearest-neighbour interaction is also supported by the mapping of the eigenvalues dynamics to the particle dynamics of calogero Hamiltonian with inverse-square interaction). As can be checked,for $`s>>\mathrm{\Lambda }`$, $`P(s,\mathrm{\Lambda })\mathrm{e}^{ks}`$ with $`k=\sqrt{\pi \mathrm{\Lambda }}`$. Near the critical point, therefore, $`k=\sqrt{\pi \mathrm{\Lambda }^{}}>1`$ and $`\chi 1/2\sqrt{\pi \mathrm{\Lambda }^{}}`$. For small separations, that is, $`s<<\mathrm{\Delta }`$, $`P(s,\mathrm{\Lambda }^{})`$ has a linear dependence on $`s`$, indicating a WD type behaviour. The spacing distribution for CSS is thus a hybrid of Poisson and WD type distributions; this result is in agreement with numerical study of .

The case of the MI transition due to off-diagonal Gaussian disorder can similarly be studied by taking finite $`\alpha _{kl}`$ values for all $`k,l`$; the $`Y`$ for any intermediate stage of the transition brought about by a most general type of diagonal and off-diagonal disorder is given by eq.(3). As obvious from the above, the presence or absence of the off-diagonal disorder will only affect the form of $`Y`$, leaving, therefore, the qualitative behaviour of various correlators unaffected. The presence of different boundary conditions (e.g. periodic) or different topology for disordered lattice will also result in different $`Y`$-values (as various $`y_{kl}`$s will be affected), leading to different level-statistics even if degree of disorder, hopping rate and dimensionality is same; this is in agreement with numerical observations .

It should be noticed here that the expressions of $`\chi (\mathrm{\Lambda })`$ as well as $`P(s,\mathrm{\Lambda })`$ are also valid for Rosenzweig-Porter (RP) ensemble ($`<H_{ii}^2>=v_1`$ for all $`i`$, $`<H_{ij}^2>=v_2`$ for all $`ij`$ and $`v_1,v_2`$ different in general), thus implying a non-zero compressibility for finite $`\mathrm{\Lambda }`$-values in RP model too contrary to earlier claims . Our result is in agreement with Dyson’s conjecture for Brownian ensembles  according to which the parameter $`\mathrm{\Lambda }`$ governs a smooth transition in fluctuation properties; the large-$`s`$ behaviour too, of $`P(s,\mathrm{\Lambda })`$, is therefore expected to vary smoothly from $`\mathrm{e}^s`$ (Poisson) to $`\mathrm{e}^{\beta s^2}`$ (Wigner).

To summarize, our analytical study shows that the statistical transition of levels of a disordered system due to change of the parameters e.g. disorder, and system size can be reduced to the transition with respect to a single scaling parameter. Our results also confirm the presence of just three type of universal statitsics for inifinite system, namely Poisson above critical value of the disorder, WD below critical value of disorder and a new type of statistics for the critical region. The critical region statistics is a hybrid of the Poisson and WD and shows a finite level compressibility. The universality of CSS is restricted in the sense that, although system-independent, it depends on the critical value $`\mathrm{\Lambda }=\mathrm{\Lambda }^{}`$ too besides the underlying symmetry of the system. We have discussed here only the $`2^{nd}`$ order level-statistics for Anderson transition. The information about the higher order correlations can be obtained from the hierarchical equation (5) for the correlators or by analyzing particle correlators of CSM Hamiltonian. Further the mapping of the level-dynamics during Anderson transition to particle-dynamics of CSM Hamiltonian once more indicates the dominance of two body interaction in nature.


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# Hyperbolic quantum mechanics

## 1 Introduction

We develop a formalism that might be called hyperbolic quantum formalism. Instead of the system of complex numbers $`𝐂,`$ we use the system of so called hyperbolic numbers111We remark that the hyperbolic arithmetics is a straightforward generalization of the complex arithmetics. Therefore this paper is quite simple from the mathematical viewpoint. We hope that it could be interesting researches working in theoretical and experimental physics. $`𝐆`$ (see, for example, , p. 21); ‘physical states’ are represented by vectors in a $`𝐆`$-Hilbert space. Generalizing Born’s probability interpretation, we found that $`𝐆`$-linear unitary transformations represent a new class of transformations of probabilities which describe a kind of hyperbolic interference:

$$𝐏^{}=𝐏_1+𝐏_2\pm 2\sqrt{𝐏_1𝐏_2}\mathrm{cosh}\theta .$$
(1)
The present formalism is nothing than a theory of hyperbolic waves of probability (compare with $`𝐂`$-quantum formalism, a theory of trigonometric waves of probability).

The most interesting problem which was generated by this investigation is to find hyperbolic interference in experiments with elementary particles (or macro systems). It might be that such results were already recoded in some experiments with elementary particles. However, they were not interpreted as an evidence of hyperbolic interference.

On the other hand, the hyperbolic quantum formalism can also be interesting as a new theory of probabilistic waves that can be developed parallely to the standard quantum theory. Comparative analysis of these two wave theories could be useful for understanding of the role of various structures of the standard quantum formalism, compare with . In particular, we reconsider the role of complex numbers in quantum theory from the purely probabilistic viewpoint. It seems that complex numbers were introduced into the quantum formalism to linearize the quantum probabilistic transformation:

$$𝐏^{}=𝐏_1+𝐏_2+2\sqrt{𝐏_1𝐏_2}\mathrm{cos}\theta .$$
(2)
The linearization is performed by the $`𝐂`$-representation of real probabilities (2) on the basis of the formula:

$$A+B+2\sqrt{AB}\mathrm{cos}\theta =|\sqrt{A}+\sqrt{B}e^{i\theta }|^2.$$
(3)
In the same way, to linearize probabilistic transformation (1) we have to use hyperbolic amplitudes:

$$A+B\pm 2\sqrt{AB}\mathrm{cosh}\theta =|\sqrt{A}\pm \sqrt{B}e^{j\theta }|^2.$$
(4)
Here $`j`$ is the generator of the algebra $`𝐆`$ of hyperbolic numbers: $`j^2=1.`$

Other distinguishing feature of the hyperbolic quantum formalism is the restricted validity of the superposition principle. A given state could not be decomposed with respect to an arbitrary complete system of other states. Of course, as in the complex case, we can always expend a vector with respect to a basis222There is some difficulty, because the system of hyperbolic numbers $`𝐆`$ is only a commutative algebra and not a number field. However, it is not so important, see  on the general theory of Hilbert modules over commutative and noncommutative algebras.. However, this operation (which is well defined from the mathematical point of view) is not always meaningful from the physical point of view. Different representations are not equivalent in the hyperbolic quantum theory.

The present note is just the first step in the development of the hyperbolic quantum formalism. It would be interesting to develop this formalism as an alternative to the standard quantum formalism. However, the most interesting problem is to find the place of hyperbolic waves of probability in experimental physics.

The main ideas on hyperbolic quantum theory were presented in author’s talk at the International Conference ”Foundations of Probability and Physics”, Växjö, Sweden-2000 (see also ). The author had numerous discussions on the origin of the quantum transformation of probabilities with J. Summhammer (see also ). I would like to thank him for these conversations.

## 2  Hyperbolic quantum formalism

1. Hyperbolic algebra. A hyperbolic algebra G is a two dimensional real algebra with basis $`e_0=1`$ and $`e_1=j,`$ where $`j^2=1.`$ Elements of G have the form $`z=x+jy,x,y𝐑.`$ We have $`z_1+z_2=(x_1+x_2)+j(y_1+y_2)`$ and $`z_1z_2=(x_1x_2+y_1y_2)+j(x_1y_2+x_2y_1).`$ This algebra is commutative. We introduce an involution in G by setting $`\overline{z}=xjy.`$ We set $`|z|^2=z\overline{z}=x^2y^2.`$ We remark that $`|z|=\sqrt{x^2y^2}`$ is not well defined for an arbitrary $`z𝐆.`$ We set $`𝐆_+=\{z𝐆:|z|^20\}.`$ We remark that $`𝐆_+`$ is the multiplicative semigroup: $`z_1,z_2𝐆^+z=z_1z_2𝐆_+.`$ It is a consequence of the equality

$`|z_1z_2|^2=|z_1|^2|z_2|^2.`$

Thus, for $`z_1,z_2𝐆_+,`$ we have $`|z_1z_2|=|z_1||z_2|.`$ We introduce

$`e^{j\theta }=\mathrm{cosh}\theta +j\mathrm{sinh}\theta ,\theta 𝐑.`$

We remark that

$`e^{j\theta _1}e^{j\theta _2}=e^{j(\theta _1+\theta _2)},\overline{e^{j\theta }}=e^{j\theta },|e^{j\theta }|^2=\mathrm{cosh}^2\theta \mathrm{sinh}^2\theta =1.`$

Hence, $`z=\pm e^{j\theta }`$ always belongs to $`𝐆_+.`$ We also have

$`\mathrm{cosh}\theta =\frac{e^{j\theta }+e^{j\theta }}{2},\mathrm{sinh}\theta =\frac{e^{j\theta }e^{j\theta }}{2j}.`$

Let $`|z|^2=x^2y^2>0.`$ We have

$`z=|z|(\frac{x}{|z|}+j\frac{y}{|z|})=\mathrm{sign}\mathrm{x}|\mathrm{z}|(\frac{\mathrm{xsignx}}{|\mathrm{z}|}+\mathrm{j}\frac{\mathrm{ysignx}}{|\mathrm{z}|}).`$

As $`\frac{x^2}{|z|^2}\frac{y^2}{|z|^2}=1,`$ we can represent $`x`$ sign $`x=\mathrm{cosh}\theta `$ and $`y`$ sign $`x=\mathrm{sinh}\theta ,`$ where the phase $`\theta `$ is unequally defined. We can represent each $`z𝐆_+`$ as

$`z=\mathrm{sign}\mathrm{x}|\mathrm{z}|\mathrm{e}^{\mathrm{j}\theta }.`$

By using this representation we can easily prove that $`𝐆_+^{}=\{z𝐆_+:|z|^2>0\}`$ is the multiplicative group. Here $`\frac{1}{z}=\frac{\mathrm{sign}x}{|z|}e^{j\theta }.`$ The unit circle in $`𝐆`$ is defined as $`S_1=\{z𝐆:|z|^2=1\}=\{z=\pm e^{j\theta },\theta (\mathrm{},+\mathrm{})\}.`$ It is a multiplicative subgroup of $`𝐆_+^{}.`$

2. Hyperbolic Hilbert space is $`𝐆`$-linear space (module) $`𝐄`$ with a $`𝐆`$-linear product: a map $`(,):𝐄\times 𝐄𝐆`$ that is

1) linear with respect to the first argument:

$`(az+bw,u)=a(z,u)+b(w,u),a,b𝐆,z,w,u𝐄;`$

2) symmetric: $`(z,u)=\overline{(u,z)};`$

3) nondegenerated: $`(z,u)=0`$ for all $`u𝐄`$ iff $`z=0.`$

Remark. If we consider $`𝐄`$ as just a $`𝐑`$-linear space, then $`(,)`$ is a bilinear form which is not positively defined. In particular, in the two dimensional case we have the signature: $`(+,,+,).`$

2. Linear space representation of states. As in the ordinary quantum formalism, we represent physical states by normalized vectors of the hyperbolic Hilbert space: $`\phi 𝐄`$ and $`(\phi ,\phi )=1.`$ We shall consider only dichotomic physical variables and quantum states belonging to the two dimensional Hilbert space. So everywhere below $`𝐄`$ denotes the two dimensional space. Let $`a=a_1,a_2`$ and $`b=b_1,b_2`$ be two dichotomic physical variables. We represent they by $`𝐆`$-linear operators: $`|a_1><a_1|+|a_2><a_2|`$ and $`|b_1><b_1|+|b_2><b_2|,`$ where $`\{|a_i>\}_{i=1,2}`$ and $`\{|b_i>\}_{i=1,2}`$ are two orthonormal bases in $`𝐄.`$

Let $`\phi `$ be a state (normalized vector belonging to $`𝐄).`$ We can perform the following operation (which is well defined from the mathematical point of view). We expend the vector $`\phi `$ with respect to the basis $`\{|b_i>\}_{i=1,2}:`$

$$\phi =\beta _1|b_1>+\beta _2|b_2>,$$
(5)
where the coefficients (coordinates) $`\beta _i`$ belong to $`𝐆.`$ As the basis $`\{|b_i>\}_{i=1,2}`$ is orthonormal, we get (as in the complex case) that:

$$|\beta _1|^2+|\beta _2|^2=1.$$
(6)
However, we could not automatically use Born’s probabilistic interpretation for normalized vectors in the hyperbolic Hilbert space: it may be that $`\beta _i𝐆_+`$ (in fact, in the complex case we have $`𝐂=𝐂_+).`$ We say that a state $`\phi `$ is decomposable with respect to the system of states $`\{|b_i>\}_{i=1,2}`$ if

$$\beta _i𝐆_+.$$
(7)
In such a case we can use Born’s probabilistic interpretation of vectors in a hyperbolic Hilbert space:

Numbers $`𝐪_i=|\beta _i|^2,i=1,2,`$ are interpreted as probabilities for values $`b=b_i`$ for the $`𝐆`$-quantum state $`\phi .`$

We now repeat these considerations for each state $`|b_i>`$ by using the basis $`\{|a_k>\}_{k=1,2}.`$ We suppose that each $`|b_i>`$ is decomposable with respect to the system of states $`\{|a_i>\}_{i=1,2}.`$ We have:

$$|b_1>=\beta _{11}|a_1>+\beta _{12}|a_2>,|b_2>=\beta _{21}|a_1>+\beta _{22}|a_2>,$$
(8)
where the coefficients $`\beta _{ik}`$ belong to $`𝐆_+.`$ We have automatically:

$$|\beta _{11}|^2+|\beta _{12}|^2=1,|\beta _{21}|^2+|\beta _{22}|^2=1.$$
(9)
We can use the probabilistic interpretation of numbers $`𝐩_{11}=|\beta _{11}|^2,𝐩_{12}=|\beta _{12}|^2`$ and $`𝐩_{21}=|\beta _{21}|^2,𝐩_{22}=|\beta _{22}|^2.`$

Remark. Let us consider matrices $`B=(\beta _{ik})`$ and $`P=(𝐩_{ik}).`$ As in the complex case, the matrice $`B`$ is unitary: vectors $`u_1=(\beta _{11},\beta _{12})`$ and $`u_2=(\beta _{21},\beta _{22})`$ are orthonormal. The matrice $`P`$ is double stochastic, namely: $`𝐩_{11}+𝐩_{12}=1,𝐩_{21}+𝐩_{22}=1`$ and $`𝐩_{11}+𝐩_{21}=1,𝐩_{12}+𝐩_{22}=1.`$

By using the $`𝐆`$-linear space calculation (the change of the basis) we get $`\phi =\alpha _1|a_1>+\alpha _2|a_2>,`$ where $`\alpha _1=\beta _1\beta _{11}+\beta _2\beta _{21}`$ and $`\alpha _2=\beta _1\beta _{12}+\beta _2\beta _{22}.`$

We remark that decomposability is not transitive. In principle $`\phi `$ may be not decomposable with respect to $`\{|a_i>\}_{i=1,2},`$ despite the decomposability of $`\phi `$ with respect to $`\{|b_i>\}_{i=1,2}`$ and the decomposability of the latter system with respect to $`\{|a_i>\}_{i=1,2}.`$

Suppose that $`\phi `$ is decomposable with respect to $`\{|a_i>\}_{i=1,2}.`$ Therefore coefficients $`𝐩_k=|\alpha _k|^2`$ can be interpreted as probabilities for $`a=a_k`$ for the $`𝐆`$-quantum state $`\phi .`$

As numbers $`\beta _i,\beta _{ik}`$ belong to $`𝐆_+,`$ we can uniquely represent them as

$`\beta _i=\pm \sqrt{q_i}e^{j\xi _i},\beta _{ik}=\pm \sqrt{p_{ik}}e^{j\gamma _{ik}},i,k,=1,2.`$

We find that

$$𝐩_1=𝐪_1𝐩_{11}+𝐪_2𝐩_{21}+2ϵ_1\sqrt{𝐪_1𝐩_{11}𝐪_2𝐩_{21}}\mathrm{cosh}\theta _1,$$
(10)
$$𝐩_2=𝐪_1𝐩_{12}+𝐪_2𝐩_{22}+2ϵ_2\sqrt{𝐪_1𝐩_{12}𝐪_2𝐩_{22}}\mathrm{cosh}\theta _2,$$
(11)
where $`\theta _i=\eta +\gamma _i`$ and $`\eta =\xi _1\xi _2,\gamma _1=\gamma _{11}\gamma _{21},\gamma _1=\gamma _{12}\gamma _{22}`$ and $`ϵ_i=\pm .`$ To find the right relation between signs of the last terms in equations (10), (11), we use the normalization condition

$$|\alpha _1|^2+|\alpha _2|^2=1$$
(12)
(which is a consequence of the normalization of $`\phi `$ and orthonormality of the system $`\{|a_i>\}_{i=1,2}).`$ It is equivalent to the equation:

$$\sqrt{p_{12}p_{22}}\mathrm{cosh}\theta _2\pm \sqrt{p_{11}p_{21}}\mathrm{cosh}\theta _2=0.$$
(13)
Thus we have to choose opposite signs in equations (10), (11). Unitarity of $`B`$ also inply that $`\theta _1\theta _2=0.`$ We recall that in the ordinary quantum mechanics we have similar conditions, but trigonometric functions are used instead of hyperbolic and phases $`\gamma _1`$ and $`\gamma _2`$ are such that $`\gamma _1\gamma _2=\pi .`$

Finally, we get that (unitary) linear transformations in the $`𝐆`$-Hilbert space (in the domain of decomposable states) represent the following transformation of probabilities:

$$𝐩_1=𝐪_1𝐩_{11}+𝐪_2𝐩_{21}\pm 2\sqrt{𝐪_1𝐩_{11}𝐪_2𝐩_{21}}\mathrm{cosh}\theta ,$$
(14)
$$𝐩_2=𝐪_1𝐩_{12}+𝐪_2𝐩_{22}2\sqrt{𝐪_1𝐩_{12}𝐪_2𝐩_{22}}\mathrm{cosh}\theta .$$
(15)
This is a kind of hyperbolic interference.333By changing hyperbolic functions to trigonometric we obtain the standard quantum interference of alternatives.

Remark. In fact, we first derived the probabilistic transformation (14), (15) by classifying possible probabilistic transformations induced by perturbation effects . Then we found the corresponding linear space representation starting with the analogy between (3) and (4).

Remark. There can be some connection with quantization in Hilbert spaces with indefinite metric as well as the theory of relativity. However, at the moment we cannot say anything definite. It seems that by using Lorentz-‘rotations’ we can produce hyperbolic interference in a similar way as we produce the standard trigonometric interference by using ordinary rotations.

References

 A. Yu. Khrennikov, Supernalysis. (Kluwer Academic Publishers, Dordreht/Boston/London, 1999).

 P. A. M. Dirac, The Principles of Quantum Mechanics. (Claredon Press, Oxford, 1995); J. von Neumann, Mathematical foundations of quantum mechanics. (Princeton Univ. Press, Princeton, N.J., 1955); E. Schrödinger, Philosophy and the Birth of Quantum Mechanics. Edited by M. Bitbol, O. Darrigol. (Editions Frontieres, 1992); J. M. Jauch, Foundations of Quantum Mechanics. (Addison-Wesley, Reading, Mass., 1968); A. Peres, Quantum Theory: Concepts and Methods. (Kluwer Academic Publishers, 1994); B. d’Espagnat, Conceptual foundations of Quantum Mechanics. (Perseus Books, Reading, Mass.,1999); P. Busch, M. Grabowski, P.J. Lahti, Operational Quantum Physics. (Springer Verlag, 1995).

 A. Yu. Khrennikov, Ensemble fluctuations and the origin of quantum probabilistic rule. Report MSI, Vaxjo University, N.90, October, (2000).

 J. Summhammer, Int. J. Theor. Physics, 33, 171-178 (1994); Found. Phys. Lett. 1, 113 (1988); Phys.Lett., A136, 183 (1989).


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# Accurate construction of transition metal pseudopotentials

## Abstract

We generate a series of pseudopotentials to examine the relationship between pseudoatomic properties and solid-state results. We find that lattice constants and bulk moduli are quite sensitive to eigenvalue, total-energy difference and tail norm errors, and clear correlations emerge. These trends motivate our identification of two criteria for accurate transition metal pseudopotentials. We find that both the preservation of all-electron derivative of tail norm with respect to occupation and the preservation of all-electron derivative of eigenvalue with respect to occupation \[Phys. Rev. B 48, 5031 (1993)\] are necessary to give accurate bulk metal lattice constants and bulk moduli. We also show how the fairly wide range of lattice constant and bulk modulus results found in the literature can be easily explained by pseudopotential effects.

Ab initio density functional theory  (DFT) calculations have been widely used over the past ten years to study transition metal surfaces and surface-adsorbate systems. The plane-wave pseudopotential (PSP) method accounts for most of these DFT calculations due to its superior speed, which allows one to study computationally intensive problems inaccessible with other methods. The absence of core electrons in the calculation and the reduced-cutoff plane-wave expansion of the PSP greatly reduce the computational cost of the solid-state calculation. Even though the PSP is required to agree with the all-electron potential outside a specified core radius ($`r_c`$), the mapping of a real, physical system onto an artificial one constructed of PSPs can introduce errors in the calculation. An ideal PSP should be completely transferable, i.e. it will mimic perfectly the behavior of the all-electron nucleus and core potential in various local chemical environments and will produce solid-state and molecular results identical to those of an all-electron calculation. Methods capable of generating transferable PSPs with small plane-wave cutoffs have been developed over the past twenty years..

It is widely assumed that the magnitude of the pseudopotential error is less than that of other approximations used in PSP-DFT calculations. Nevertheless, some fundamental questions regarding PSP construction remain unresolved. While it is accepted that a PSP must preserve certain all-electron properties to be considered transferable, it is unclear which all-electron properties are vital.

Various criteria for comparing PSP results to those of an all-electron potential have been proposed, such as agreement between all-electron and PSP eigenvalues along with total-energy differences, norm-conservation at the reference configuration and preservation of logarithmic derivatives at $`r_c`$ and the correct chemical hardness matrix.  Eigenvalue and total-energy difference agreement are the most often used criteria for determining if a PSP is transferable. However, no clear correlation has been firmly established between these criteria and solid-state results. The determination of PSP quality is further confused by the fact that a simple comparison with experiment sometimes cannot be used to gauge PSP quality. For example, since the local-density approximation (LDA) overbinds, an LDA-PSP calculation that predicts the experimental value for the lattice constant is less accurate than an LDA-PSP calculation that slightly underestimates the bulk lattice constant.

Bulk lattice constants and moduli are often used to assess the quality of a PSP. These parameters can now be easily determined due to powerful computers and fast DFT packages. PSP construction is also a fairly routine procedure due to the availability of various efficient PSP generation codes. The PSP transferability error is widely considered to be insignificant compared to other approximations used in PSP-DFT calculations, such as the choice of the exchange-correlation functional. Yet, surveying the ab initio PSP-DFT calculations performed in the past five years on various transition metals, transition metal surfaces and adsorbate systems, one finds a broad distribution in predicted lattice constants and bulk moduli for both LDA and generalized gradient approximation (GGA) calculations , with variations in results being greater than that caused by the use of different exchange-correlation functionals. Lattice constant errors in published LDA calculations vary from -1.3$`\%`$  to +0.3$`\%`$  to +1.6$`\%`$  for rhodium and from -1.0$`\%`$  to -0.7$`\%`$  to +1.7$`\%`$  for silver. For bulk ruthenium metal, GGA lattice constants with errors of +1.5$`\%`$ , +2.0$`\%`$  and +3.0$`\%`$  have been calculated. For a wide range of materials, it is known that LDA underestimates bond lengths somewhat, while GGA slightly overestimates bond lengths. Nevertheless, many PSP-DFT studies on transition metals in the literature use LDA PSPs that give lattice constants larger than experiment, sometimes by as much as 1$`\%`$ While the LDA lattice constant errors in the literature are typically between -1$`\%`$ to +1$`\%`$, bulk moduli are overestimated by up to 30$`\%`$ The use of GGA functionals reduces the tendency to overbinding, so the range of GGA error in reported calculations shifts to 0$`\%`$ to 3$`\%`$ error in the lattice constant and -10$`\%`$ to 10$`\%`$ error in the bulk modulus.  The inability of the otherwise reliable PSP-DFT methods to correctly and consistently predict these simple quantities is puzzling. Since the methods as well as the exchange-correlation functionals used to obtain these bulk parameters are identical or very similar for all of these studies, much of the variation in the literature must be due to the use of different PSPs.

In order to find the possible sources of PSP error and to test for correlations between these errors and errors in the solid-state results, we must examine the PSP construction procedure. An ideal PSP should reproduce the all-electron wave functions beyond $`r_c`$ for all atomic configurations. Enforcing eigenvalue agreement for all atomic configurations will not necessarily enforce wave function agreement. Although the eigenvalue governs the rate of exponential decay of both the all-electron and pseudo-wave functions, the prefactors multiplying the exponentials may be different. This will lead to either underestimation or overestimation of the charge in the tail of the wave function, and the incorrect distribution of charge on the atomic level will lead to inaccuracies in the solid-state properties. The widely used norm-conserving PSP construction methods enforce agreement of the wave function norm for the reference configuration only. Therefore, norm conservation and eigenvalue agreement in configurations other than the reference configuration are important for PSP transferability, and both must be checked to gauge the quality of the PSP at the atomic level. This is an extension of the original idea of Hamann, Schlüter and Chiang in their landmark paper on norm-conserving PSPs.  They showed that enforcing norm conservation at the reference configuration dramatically improved PSP quality. In this paper, we demonstrate that the failure to conserve norm in configurations other than the reference configuration leads to significant transferability errors, and we propose a new atomic transferability criterion which leads to more accurate atomic and solid-state results.

The designed nonlocal (DNL) PSP construction approach  allows us to adjust the amount of PSP norm and eigenvalue error in various atomic configurations, while leaving the agreement at the reference configuration unchanged. We can, therefore, systematically introduce errors in different proposed transferability criteria to examine the consequences of PSP error in solid-state calculations. We can then approximately enforce these new criteria and determine whether accuracy tracks quantitatively with criterion enforcement.

In solids, the interatomic potential can be heuristically described as the sum of an attractive bonding term and repulsive Pauli and electrostatic interaction terms. The balance between these terms leads to an equilibrium lattice constant, and a change in either the repulsive or the attractive part of the potential will change the solid-state bulk properties of the crystal. Increasing the amount of charge in the tail region will strengthen the interatomic repulsive potential, expanding the equilibrium lattice constant of the crystal. In the same way, decreasing the charge in the tail will contract the crystal. Errors in the eigenvalues and total-energy differences affect the attractive bonding term of the solid-state interatomic potential. The total-energy differences between the various atomic configurations are related to $`d`$$``$$`s`$ excitation energies, which govern the extent of $`sd`$ hybrid orbital formation in solids. An overestimation of the $`d`$$``$$`s`$ excitation energy implies an increase in the hybridization energy cost, leading to a weaker bonding term and expansion of the crystal. Conversely, underestimation of $`d`$$``$$`s`$ excitation energy will lead to contraction of the crystal.

To verify our understanding of how norm-conservation and eigenvalue agreement affect solid-state results, we examine six different Rh PSPs. The $`d`$-states are more populated than the $`s`$-states in the right half of the $`d`$-block of the Periodic Table and unlike the $`s`$-states, the $`d`$-states are localized on individual atoms in the solid state. We therefore will focus on the norm of the $`d`$-states. We also compare eigenvalues and total-energy differences. All calculations are done using the Perdew-Burke-Ernzerhof GGA  exchange-correlation functional at a plane-wave cutoff of 50 Ry. For all six PSPs, we compute eigenvalues, total-energy differences, and norms of the tail region ($`r`$ $``$ 2.6 Bohr) for three sample configurations: $`s^0p^0d^9`$, $`s^1p^0d^8`$ and $`s^2p^0d^7`$. For comparison, we also compute the corresponding all-electron values in the three sample configurations. These configurations span the spectrum of neutral Rh states important in the bulk metal solid. PSPs RhA, RhB, RhC, RhD and RhE were created in a +0.1 ionized reference configuration ($`s^0p^0d^{8.9}`$) by gradually varying the depth of the DNL augmentation operator $`\widehat{A}`$. PSP RhA preserves all-electron $`d`$-state norms and eigenvalues and total-energy differences, PSP RhB and PSP RhC are constructed to match the all-electron $`d`$-state norms but not the eigenvalues and total-energy differences, and PSP RhD is constructed so that the eigenvalues and total-energy differences match the all-electron results, but the $`d`$-state norms do not. PSP RhE is constructed to give a lattice constant error of +2$`\%`$ typical for GGA calculations found in the literature. PSP RhF was created in a +1.7 ionized reference configuration ($`s^{0.1}p^{0.1}d^{7.1}`$) and $`\widehat{A}`$ was adjusted until solid-state calculations gave a -0.2$`\%`$ error in the lattice constant. PSP RhF has large errors in both eigenvalue and total-energy differences and norms but gives a lattice constant similar to that of PSP RhA. The results for the six PSP’s as well as all-electron values are in Table I.

Examination of the results for PSPs RhA and RhD in Table I shows that underestimation of charge in the tail region ($`r`$ $``$ 2.6 Bohr) decreases the solid-state lattice constant. Despite having very similar eigenvalues to PSP RhA, pseudo-wave functions of PSP RhD are shifted inward as shown by the negative norm error. This makes the repulsive term in the interatomic potential smaller, resulting in a smaller lattice constant in the solid state. The results in Table I also confirm the importance of eigenvalue and total-energy difference agreement and the connection between $`d`$$``$$`s`$ excitation energies and solid-state lattice constant. A comparison of PSP RhA and PSP RhB shows that an average increase in $`d`$-eigenvalue error of only 2.0 mRy per configuration and total-energy difference error of about 1.0 mRy per configuration leads to an expansion of the crystal by about 0.8$`\%`$. An overestimation of the $`d`$$``$$`s`$ excitation energy by PSP RhB implies an increased hybridization energy cost. This means that PSP RhB will underestimate the attractive bonding energy term, leading to an overestimation of the lattice constant. On the other hand if the hybridization energy is underestimated, the attractive bonding term will be larger and the lattice constant will be smaller. In the case of PSP RhC, average $`d`$-eigenvalue error of +5.0 mRy per configuration and average total-energy difference error of about -3.6 mRy per atom leads to a contraction of the crystal, giving an error of -2.3$`\%`$ in the lattice constant. Not only the direction but also the magnitude of the lattice constant error for PSP RhB and PSP RhC track with the respective total-energy difference errors. Since many GGA calculations in the literature overestimate the lattice constant by 2$`\%`$, we created PSP RhE to show that this could be accounted for by pseudopotential effects. An overestimation of the $`d`$$``$$`s`$ excitation energy by an average of 3.2 mRy is all that is required to cause the 2$`\%`$ expansion in the solid state.

An accurate GGA lattice constant can be obtained even by a PSP with incorrect bonding and repulsion terms, if the two errors cancel. However, the errors will not cancel out for the bulk modulus. If interatomic attraction and repulsion are equally overestimated, the potential well will be steeper, resulting in a significant overestimation of bulk modulus. To examine this effect we can compare the data for PSPs RhA and RhF. The lattice constant error is very small for both potentials, which is what we expect from GGA calculations. However PSP RhF has significant eigenvalue, total energy and norm transferability errors. The error in the bulk modulus changes considerably from PSP RhA to PSP RhF. As can be seen from the data, the $`d`$$``$$`s`$ excitation energy is significantly underestimated, leading to greater attractive bonding energy and consequently smaller lattice constant. However more charge in the tail region (shown by increased norms in sample states) leads to a greater repulsive potential and cancels out the effect of the eigenvalue/total-energy difference error. The steeper potential that is produced by the combination of the two effects results in the overestimation of the bulk modulus for PSP RhF. Superficially, PSP RhF seems superior to PSP RhA due to smaller bulk modulus error. However, the better comparison with experiment is due to a fortuitous cancellation of pseudopotential and GGA functional errors which will not necessarily be favorable in calculations for other solid-state properties.

While the eigenvalue and norm-conservation errors are comprehensive quantities (i.e. sums over various atomic configurations), the derivative of the amount of charge in the tail region in state $`i`$ ($`N_i`$) with respect to occupation of state $`j`$ $`\left(\frac{dN_i}{df_j}\right)`$ and the derivative of eigenvalue of state $`i`$ with respect to occupation of state $`j`$ $`\left(\frac{d\epsilon _i}{df_j}\right)`$ are properties of the reference configuration only, making them more amenable to enforcement in the PSP construction. These two tensors are also good predictors of norm-conservation and eigenvalue error in sample configurations. It has been shown  that $`\frac{d\epsilon _i}{df_j}`$ (the chemical hardness) is important for transferability.

In this work we confirm the importance of $`\frac{d\epsilon _i}{df_j}`$ conservation while adding $`\frac{dN_i}{df_j}`$ as a second transferability criterion. To show how the quality of PSP $`\frac{dN_i}{df_j}`$ and $`\frac{d\epsilon _i}{df_j}`$ affect solid-state accuracy we create a PSP quality correlation map for Rh (Figure 1) . The PSPs were created in various reference configurations ranging from +1.7 ionized to neutral with various $`r_c`$’s, plane-wave cut-off energies and augmentation operators. The abscissa of Figure 1 is the error in $`\frac{d\epsilon _i}{df_j}`$ and the ordinate is the error in $`\frac{dN_i}{df_j}`$. The quality of each potential is evaluated based on the lattice constant and bulk modulus obtained from solid-state DFT calculations. It can be seen that the best PSPs (those with small error in $`\frac{dN_i}{df_j}`$ and $`\frac{d\epsilon _i}{df_j}`$) fall close to the origin, while a deviation in either of the atomic quantities strongly degrades solid-state results. This confirms the importance of these two criteria, and therefore both should be included in PSP construction.

We have found these same trends in calculations using the LDA exchange-correlation functional  and in calculations on other transition metals including Ru, Pd, Pt, Cu, Ag and Au. Chemisorption energies of atoms and molecules on transition metal surfaces obtained by PSP-DFT calculations will also be affected by PSP error due to the strong dependence of the chemisorption energy on lattice constant .

In this paper, we have presented results for bulk Rh metal properties calculated with the GGA exchange-correlation functional. We constructed a family of Rh pseudopotentials with various eigenvalue, total-energy difference and tail norm conservation properties. We then calculated lattice constants and bulk moduli for each pseudopotential to gauge how the atomic level errors correlate with the results of the solid-state calculations. We found that the bulk solid-state properties are very sensitive to the choice of pseudopotential. The range of the results given by various PSPs (-2.3$`\%`$ to +2.0$`\%`$) is considerably larger than the commonly assumed range of results given by various exchange-correlation functional approximations. We find that simultaneously enforcing agreement between all-electron and pseudopotential $`\frac{dN_i}{df_j}`$ and $`\frac{d\epsilon _i}{df_j}`$ greatly reduces Rh pseudopotential error, leading to lattice constant which is slightly larger than experiment and a bulk modulus which is somewhat smaller than experiment. We show that the simultaneous enforcement of $`\frac{dN_i}{df_j}`$ and $`\frac{d\epsilon _i}{df_j}`$ agreement will give accurate bonding and repulsive forces leading to accurate solid-state properties.

This work was supported by NSF grant DMR 97-02514 and the Office of Naval Research grant No. N-00014-00-1-0372. AMR acknowledges the support of the Camille and Henry Dreyfus Foundation. Computational support was provided by the San Diego Supercomputer Center and the National Center for Supercomputing Applications.