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# 1. Introduction

## 1. Introduction

The gravitational scalar field, sometimes called the dilaton of a likely origin in string theory, is a focus of attempts to understand the small but nonzero cosmological constant . The fast-falling potential, like the exponential or the inverse-power type, has been favored either in phenomenological analyses  or as models of theoretical interest \[3-6\]. In particular we have studied the exponential potential in the context of the scalar-tensor theory with the constant $`\mathrm{\Lambda }`$ included . It seems agreed that the global behavior of the spatially-uniform solution for the scalar field that allows us to implement the scenario of a decaying cosmological constant is consistent with “masslessness” of the field, in the sense that its inverse “mass” is as large as $`t_0`$, the present age of the universe, or the size of the visible universe.

Some of the authors go even further to argue that the field mediates a long-range force between macroscopic objects around us, thus is subject to the solar-system experiments, or some free-fall measurements above the detectable level . The present author, on the other hand, emphasizes that the spatially-dependent component results more likely in the local force with a finite and intermediate force-range, as also discussed in , not necessarily constrained by the above mentioned experiments . In this article we try to reinforce the latter point of view, expressed rather vaguely in the middle of Chapter 6.4 of , by the detailed analysis of the self-energy of the quantized scalar field arising from the interaction with matter fields.

The root of the issue lies in the widely accepted view that, unlike a gauge field, the scalar field shows no immunity against acquiring self-mass due to the interaction. We recognize, on the other hand, that the vacuum-energy in the sense of the relativistic quantum field theory predicts too much contribution to the cosmological constant, and appears to be suppressed almost to zero according to the observation. We show how the latter fact is related to the present issue, also discussing what the theoretical formulation should be like in order to have the expected distinction between the global and local aspects. We admit that the conclusion, partly a conjecture, is still tentative depending to some extent on the specific model chosen. We still believe the effort to provide an important insight to the issue.

## 2. Preliminaries

We start with the 4-dimensional Lagrangian of the scalar-tensor theory with the constant $`\mathrm{\Lambda }`$ included in the J(ordan) conformal frame (CF), sometimes called the string CF, or the theoretical CF:

$$=\sqrt{g}\left(\frac{1}{2}\xi \varphi ^2R\frac{1}{2}ϵg^{\mu \nu }_\mu \varphi _\nu \varphi \mathrm{\Lambda }+L_{\mathrm{matter}}\right),$$
(1)
where $`\varphi `$ is the scalar field, while $`\xi `$ and $`ϵ`$ are related to $`\omega `$ in the prototype Brans-Dicke model by $`\xi ^1=4|\omega |>0`$ and $`ϵ=\text{Sign}(\omega )`$. Notice that choosing $`ϵ=1`$ implies a ghost with negative kinetic energy of $`\varphi `$, but, due to the “mixing” effect in the non-minimal coupling term, the first term on the right-hand side of (1), the total energy remains positive as long as $`\zeta ^26+ϵ\xi ^1=2(3+2\omega )>0`$, assumed also of the order unity. We use the (reduced) Planckian unit system with $`c=\mathrm{}=M_\mathrm{P}(=(8\pi G/c\mathrm{})^{1/2})=1`$. Note that $`\mathrm{GeV}=0.41\times 10^{18}`$ while the present age of the universe $`t_014\mathrm{G}\mathrm{y}`$ is $`1.66\times 10^{60}`$. To make the paper to be minimally self-contained, we summarize the formulation briefly according to , though some of the contents had been obtained in \[3-5\] in different contexts.

The cosmological constant problem has two faces : “Why is it so small compared with $`M_\mathrm{P}^4`$?” and “Why is it still nonzero?” In this note we confine ourselves to the first one, which is replied successfully by showing that the effective cosmological constant decays with the cosmic time. Including a constant $`\mathrm{\Lambda }`$ on the right-hand side of (1), however, changes the cosmological solution without $`\mathrm{\Lambda }`$ so drastically that many traditional views deviate dangerously from what the standard cosmology has told us. In our proposed remedy , we allow the scalar field to enter $`L_{\mathrm{matter}}`$, thus violating Weak Equivalence Principle, but in such a way that its observable effects remain relatively small. In this “scale-invariant model,” scale invariance observed by the first two terms on the right-hand side of (1) is extended to the matter part.

* In the prototype BD model, $`L_{\mathrm{matter}}`$ is assumed to be decoupled from $`\varphi `$ in the J frame. We revise this by introducing a term $`(1/2)f^2\varphi ^2\mathrm{\Phi }^2`$, where $`\mathrm{\Phi }`$ is a real scalar field as a representative of matter fields throughout this paper, not to be confused with the gravitational $`\varphi `$, while $`f`$ is a dimensionless coupling constant. No mass term of $`\mathrm{\Phi }`$ is assumed at this stage.
* By applying a conformal transformation moving to the E(instein) CF, the above-mentioned interaction term becomes a mass term, $`(1/2)m^2\mathrm{\Phi }_{}^2`$ with $`m^2=\xi ^1f^2`$, with the scalar field left entirely decoupled from the matter field $`\mathrm{\Phi }_{}`$. Scale invariance is shown to be broken spontaneously with the canonical $`\sigma =\zeta ^1\mathrm{ln}(\xi ^{1/2}\varphi )`$ as a massless Nambu-Goldstone boson. We may accept this E frame to be a physical CF.
* By including quantum corrections among matter fields, the $`\sigma `$-matter coupling re-emerges as an effect of quantum anomaly:

$$L^{}=\frac{1}{2}g_\sigma \mathrm{\Phi }_{}^2\sigma ,\text{with}g_\sigma =\zeta Qm^2M_\mathrm{P}^1,$$
(2)
to the one-loop approximation, where $`Q`$ is a coefficient which depends on the non-gravitational coupling constants of the matter fields, WEP thus being violated. The factor $`M_\mathrm{P}^1`$ has been re-installed as a reminder that $`g_\sigma `$ has mass dimension 1. Scale invariance is now broken explicitly, leaving $`\sigma `$ as a pseudo NG boson, which is generically massive. We point out that the calculation was made in the dimensional regularization method which is different from a simple cutoff procedure .

Let us ignore the quantum effects for the moment, and re-express (1) in terms of the starred quantities in the E frame:

$$=\sqrt{g_{}}\left(\frac{1}{2}R_{}\frac{1}{2}g_{}^{\mu \nu }_\mu \sigma _\nu \sigma \mathrm{\Lambda }e^{4\zeta \sigma }+L_{\mathrm{matter}}\right).$$
(3)
Note that the constant term $`\mathrm{\Lambda }`$ in (1) has been transformed to an exponential potential, $`V(\sigma )=\mathrm{\Lambda }e^{4\zeta \sigma }`$. In the Friedmann universe with $`k=0`$, the cosmological equations are

$`3H_{}^2`$ $`=`$ $`\rho _\sigma +\rho _{},`$ (4)
$`\ddot{\sigma }`$ $`+`$ $`3H_{}\dot{\sigma }+V^{}(\sigma )=0,`$ (5)
where we assumed radiation dominance to simplify the equations, though the conclusion remains essentially unchanged for dust dominance as well. We also use the over-dot for differentiation with respect to $`t_{}`$, the cosmic time in the E frame, while $`\rho _\sigma =\dot{\sigma }^2/2+V(\sigma )`$, representing “dark energy,” plays the role of an effective cosmological “constant” $`\mathrm{\Lambda }_{\mathrm{eff}}`$ in the E frame. On the other hand, $`\rho _{}`$ is the energy density of the matter including dark matter.

We find the solution for the spatially uniform $`\sigma `$:

$$\sigma (t_{})=\overline{\sigma }+\frac{1}{2}\zeta ^1\mathrm{ln}t_{},$$
(6)
where $`\overline{\sigma }`$ is a constant determined by $`\mathrm{\Lambda }e^{4\zeta \overline{\sigma }}=(1/16)\zeta ^2`$. This describes a slowly-rolling-down behavior, and is an attractor solution independent of the initial values. We also obtain

$`\rho _\sigma `$ $`=`$ $`{\displaystyle \frac{3}{16}}\zeta ^2t_{}^2,`$ (7)
$`\rho _{}`$ $`=`$ $`{\displaystyle \frac{3}{4}}\left(1{\displaystyle \frac{1}{4}}\zeta ^2\right)t_{}^2.`$ (8)
Note that these asymptotic behaviors are independent of $`\mathrm{\Lambda }`$. Equation (7) shows that $`\mathrm{\Lambda }_{\mathrm{eff}}`$ falls off like $`t_{}^2`$, implementing the decaying $`\mathrm{\Lambda }`$ scenario. Note that the common “scaling” behavior as in (7) and (8) provides short of understanding the “second face,” requiring a further attempt, like the “two-scalar model” .

The potential has no minimum. One may nevertheless define a “mass squared” by

$$\mu _b^2=\frac{^2V}{\sigma ^2}=(4\zeta )^2V.$$
(9)
By using (6) we immediately find $`Vt_{}^2`$. Combining this with (9) we conclude

$$\mu _b^2t_{}^2,$$
(10)
up to the multiplying coefficient roughly of the order unity. At the present epoch, the mass $`\mu _b`$ is as small as $`t_0^1`$, or the “force-range” as large as $`t_0`$, which is the size of of the visible universe. We may consider that $`\sigma _b`$ is “massless” in any practical situation.

The fact that the right-hand side of (9) is positive implies a restoring force for any small deviation of $`\sigma _b`$ from the solution (6). This can be combined with the presence of the frictional force given by the second term on the left-hand side of (5) supporting that this solution is stable against the small perturbation of the mass squared given by (10).

## 3. Background and fluctuation

One might then be tempted to consider the exchange of this field to provide a long-range force in practice. We point out, however, that the spatially-independent field is totally alienated from the concept of a force that attracts or repels two objects. In order to discuss a force we must include spatially-varying portion as well. For this purpose, we consider the decomposition:

$$\sigma (x)=\sigma _b(t)+\sigma _f(x).$$
(11)
Substituting this into (3), we would find the coupled equations for $`\sigma _b`$ and $`\sigma _f`$ for the background and the fluctuating components, respectively. The way in which the one affects the other is found to be largely asymmetric. Roughly speaking, $`\sigma _f`$ remains nearly unaffected by $`\sigma _b`$, while opposite in the other way. This can be seen qualitatively by looking at the kinetic term on the right-hand side of (3), which is split into

$$\frac{1}{2}(\sigma _b)^2(\sigma _b\sigma _f)\frac{1}{2}(\sigma _f)^2.$$
(12)
The last term is expected to be of the order of $`\stackrel{>}{}\mu _f^2`$, with $`\mu _f`$ being the self-mass of $`\sigma _f`$, which will be estimated to be somewhere around $`\mu _fm^2/M_\mathrm{P}10^{18}\mathrm{GeV}10^{36}`$ where $`m\mathrm{GeV}10^{18}`$ is a typical hadronic mass . By using (6), on the other hand, we expect that the first and the second terms are of the size of $`t_0^2`$ and $`t_0^1\mu _f`$, and are smaller than the last term by 48 and 24 orders of magnitude, respectively. In the subsequent analyses we confine ourselves entirely to the E frame, suppressing $``$ to simplify the notation.

In order to outline a possible theoretical approach, we present the argument in two steps; (i) showing how $`\sigma _f`$ is quantized then acquiring mass, (ii) discussing what kind of back-reaction $`\sigma _b`$ can be subject to.

## 4. Quantizing the fluctuating part

The potential for $`\sigma _f`$ is given by

$$V\left(\sigma _b+\sigma _f\right)\frac{1}{16}\zeta ^2t_0^2e^{4\zeta \sigma _f},$$
(13)
where we have used $`V(\sigma _b)=(1/16)\zeta ^2t_0^2`$ for $`tt_0`$ as derived from (6).

The exponential potential allows no stationary point $`dV/d\sigma _f=0`$ to occur. But this “tilt” as well as “curvature,” both proportional to $`t_0^2`$, are again so small that any local experiments or observations, like measuring a $`\sigma _f`$-exchanged force between two objects, have no resolving capability to detect them. In this approximate and realistic situation, $`\sigma _f`$ is well separated from $`\sigma _b`$, thus behaving as a massless scalar field, with

$$L_f=\frac{1}{2}(\sigma _f)^2,$$
(14)
which provides a classical theory based on which perturbative quantum theory around the present epoch is to be developed.

Now according to the relativistic quantum field theory on nearly flat spacetime, the interaction (2) with the matter field $`\mathrm{\Phi }`$, which is otherwise assumed to be free, yields a tadpole:

$$𝒯=g_\sigma i(2\pi )^4d^4k\frac{1}{k^2+m^2},$$
(15)
also depicted in Fig. 1(a). The integral is divergent by power counting, but is probably cut off at some mass-scale basically of the order of magnitude not very much different from $`m`$, thus

$$𝒯m^4,$$
(16)
which is $`10^{72}`$, allowing a latitude of a few orders of magnitude.

We next consider the self-energy part $`\mathrm{\Pi }(p^2)`$ of the quantized field $`\sigma _f`$ coming from the $`\mathrm{\Phi }`$ loop, as shown by Fig. 1(b):

$$\mathrm{\Pi }(p^2)=g_\sigma ^2𝒥(p^2),$$
(17)
with

$`𝒥(p^2)`$ $`=`$ $`i(2\pi )^4{\displaystyle d^4k_1d^4k_2\frac{\delta ^4(k_1+k_2p)}{(k_1^2+m^2)(k_1^2+m^2)}},`$ (18)
$`=`$ $`{\displaystyle \frac{1}{\pi }}{\displaystyle _{s_0}^{\mathrm{}}}{\displaystyle \frac{\rho (s^{})}{s^{}siϵ}}𝑑s^{},`$
where $`s=p^2=p_0^2\stackrel{}{p}^2`$ with $`\rho (s)=(16\pi )^1\sqrt{1s_0/s}=k/(8\pi W)`$, where $`W=\sqrt{s}`$ is the total energy of the pair of $`\mathrm{\Phi }`$, $`k`$ and $`s_0=4m^2`$ are the relative momentum and the threshold energy squared, respectively.

Following the usual procedure, $`\mathrm{\Pi }`$ evaluated at $`p^2=\mu _f^2`$ will give a self-mass squared $`\mu _f^2`$, which is assumed to be positive. It also seems reasonable to expect that $`\mu _f^1`$ is of a macroscopic size certainly shorter than the distances relevant to the solar-system experiments .

## 5. Back-reaction to the background part

We started by accepting the solution (6) to be a classical background solution. As explained before, however, the back-reaction from the quantized $`\sigma _f`$ might be serious. One might be forced even to include “own virtual quantum processes ” of $`\sigma _b`$, despite its huge macroscopic size which may justify the classical nature. A self-consistent way of solving the equations seems imperative, as shown by a field theoretical analysis of the non-equilibrium Bose-Einstein condensate , for example. This is a feature to be supplemented to the formal procedure described on the use of the nontrivial classical background field .

The field $`\sigma _b`$ thus acquires the same tadpole term as (15) and (16), because the coupling (2) has been derived for the entire sum (11) of $`\sigma `$. The result (16) is then added to the “slope”

$$\frac{V}{\sigma }=4\zeta V(\sigma _b(t_0)),$$
(19)
which is $`t_0^2`$, as estimated in (9) and (10), being smaller than the “correction” (16) by as much as 48 orders of magnitude.

This is a place where one might give up the whole attempt to successfully implement the scenario of a decaying $`\mathrm{\Lambda }`$. According to the conventional renormalization program, however, the “divergent” term is replaced by the “observed” value. Equivalently, one has a freedom to add a counter-term $`𝒞_1`$ to obtain the observed value $`𝒱_1=4\zeta V+𝒯+𝒞_1`$. Unfortunately, no appropriate “observation” is available for the scalar field. We find, however, a substitute from another phenomenon of different but related kind.

We re-emphasize that $`\sigma _b(t)`$ is spatially constant and the energy density computed as the quantum corrections to $`V(\sigma _b)`$ as shown in Fig. 1, with the dotted line for the small perturbation of $`\sigma _b`$, is distributed uniformly in the universe, thus constituting part of the cosmological “constant” at the epoch $`t`$. Obviously this is part of the vacuum-energy without the external matter field $`\mathrm{\Phi }`$. On the other hand, the observed vacuum-energy contribution to the cosmological constant is known to be smaller than the theoretical prediction by about “60” orders of magnitude , which is basically the same as the number 48 derived before, in view of uncertainties in the estimates. We now propose to use this “suppression” as the “observed value” for the back-reaction effect to $`V(\sigma _b)`$.

Toward the end of Chapter 4.4.2 of , we offered a conjecture that no discrepancy of “60” orders of magnitude mentioned above might occur if the vacuum-energy builds up gradually starting from an infinitesimal amount in the expanding universe, unless no ingredient of the vacuum-energy is time-dependent, allowing the expression $`g_{\mu \nu }\times \mathrm{const}`$ in the E-frame Lagrangian. This is in fact what we usually do for the matter density arriving at an asymptotic behavior $`t^2`$ like in (8), with an added reminder that we thereby must have included the vacuum-energy as well, although it could act as a cosmological “constant” only if it falls off at least more slowly than $`t^2`$.

We note that the spatially-averaged cosmological matter density has no distinction between vacuum- and non-vacuum-energies, perhaps up to different equations of state. In any case it seems highly unlikely that the vacuum-energy component, whether it behaves like a constant or not, grows overwhelmingly beyond the critical density at the expense of the non-vacuum energy. The vacuum-energy must be suppressed below the level $`t_0^2`$ for whatever the reason yet to be elaborated. According to our proposal, the tadpole term $`m^4`$ should be renormalized to a value $`\stackrel{<}{}t_0^2`$:

$$𝒱_1\stackrel{<}{}4\zeta V,$$
(20)
implying that $`𝒞_1`$ is adjusted to cancel most of $`𝒯`$, probably exploiting the smallness of $`t_0^1`$ by appealing to a cosmological argument.

A more careful analysis is needed for the self-energy part $`\mathrm{\Pi }`$, because it has a spatial extension much smaller than $`t_0`$. For this purpose we use the spectral representation  given by the second line of (18) which is convenient because the spatial Fourier transform $`𝒥(r)`$ is given in terms of the superposition of the Yukawa terms:

$$𝒥(r)=\frac{1}{4\pi ^2}\frac{e^{\kappa r}}{r}\rho (s)𝑑s,$$
(21)
where $`\kappa =\sqrt{s}`$. We estimate

$$\mathrm{\Pi }(r)A\frac{g_\sigma ^2}{4\pi ^2}m^2\frac{e^{2\overline{m}_1r}}{4\pi r},$$
(22)
where $`A`$ is a coefficient of the order one, while $`\overline{m}_1`$ is somewhere between $`m`$ and $`m_1`$ below which $`s`$ can be approximated by $`4m^2`$, hence chosen roughly to be $`m`$.

We consider Dyson’s equation:

$$\mathrm{\Delta }^1=\mathrm{\Delta }^1<\mathrm{\Pi }>,$$
(23)
where the zero-th order term $`\mathrm{\Delta }^1=\mu _b^2t_0^2`$ is a constant for the spatially non-propagating field, while the last term on the right-hand side is for an “average” $`<\mathrm{\Pi }>=𝑑\stackrel{}{r}\mathrm{\Pi }(\stackrel{}{r})`$. On integrating (22) we find $`𝑑\stackrel{}{r}r^1e^{r/\lambda }\lambda ^2,`$ where $`\lambda (2\overline{m}_1)^1m^1`$. In this way we obtain

$$<\mathrm{\Pi }>m^6\lambda ^2m^4,$$
(24)
which is “large” in the same order of magnitude as in (16). Nearly the same argument as the tadpole term applies again.

Unlike with the tadpole, however, the function $`\mathrm{\Pi }`$ depends on $`p^2`$. The above-mentioned suppression is related to the global structure, and applies only to $`p^2t_0^2`$, leaving the value for $`p^2\mu _f^2`$ obtained from the quantized component almost unaffected. This scenario, which is yet to be justified rigorously, should make the two aspects compatible to each other; massless global field and massive local field. One might interpret this also as a “running” counter-term which varies toward $`p^2t_0^2`$ in a non-trivial manner, represented symbolically by

$$𝒞_2(t_0^2)\mathrm{\Pi }(t_0^2),\text{and}𝒞_2(\mu _f^2)\mathrm{\Pi }(\mu _f^2).$$
(25)
How good the first approximate equation is would determine how close the resulting potential is to the original one. This requires a more precise analysis based on the standard renormalization procedure. On the other hand, the “observed” suppression of the vacuum energy in the cosmological constant might be so strong, as expressed by the number “60” orders of magnitude, that the whole “correction,” including the counter terms, to $`V(\sigma _b)`$ can be made negligibly small. In this simplest imaginable but still likely situation, the exponential potential remains virtually unaffected, no matter how complicated the detailed renormalization procedure might be.

Similar analyses on the higher-order terms of $`\sigma _b`$, like the one illustrated by Fig. 1(c), should be subject to the same kind of suppression required for all the terms, in order to maintain the exponential potential. This necessity on the finite-part renormalization might appear too artificial, but is supported by the suppression of all kinds of the vacuum-energy. It is rather natural after all to expect that the influence of the unique nature of $`\sigma _b`$ which extends globally to the whole universe overrides consequences of the local physics of the quantized component as far as the global aspect is concerned.

## 6. Concluding remark

We have shown that globally massless and locally massive behaviors of a single field dilaton can be consistent with each other. Although the conclusion is not unique, this feature is related closely to another theoretical question why the vacuum-energy expected naturally from the quantum field theory in Minkowskian spacetime predicts too much excess compared with the observation. We re-iterate that we have only outlined what the theory should be like. Solving the equations for $`\sigma _b`$ and $`\sigma _f`$ more rigorously should be made only if we establish a detailed mechanism to suppress the vacuum-energy. This will be a key to understand the whole problem of the cosmological constant including the scenario of a decaying $`\mathrm{\Lambda }`$ for the component of the primordial origin.

I thank Thibault Damour whose comment on the occasion of JENAM 2002 in Porto-Portugal motivated this work. Thanks are also due to Y. Chikashige, R. Fukuda, S. Ichinose, S. Kamefuchi, K. Kawarabayashi, K. Maeda, H. Matsumoto and M. Omote for their enlightening discussions.

References

1. A.G. Riess et al., Astgron. J. 116, 1009 (1998); S. Perlmutter et al., Nature, 391, 51 (1998).
2. B. Ratra and P.J.E. Peebles, Phys. Rev. D37, 3406 (1988); R.R. Caldwell, R. Dave and P.J. Steinhardt, Phy. Rev. Lett. 80, 1582 (1998); L. Wang, R.R. Caldwell, J.P. Ostriker, P.J. Steinhardt, Astrophys.J. 530, 17 (2000).
3. J. Yokoyama and K. Maeda, Phys. Lett. B207, 31 (1988).
4. C. Wetterich, Nucl. Phys. B302, 645 (1988).
5. C. Wetterich, Nucl. Phys. B302, 668 (1988).
6. T. Damour, F. Piazza and G. Veneziano, Phys. Rev. Lett. 89, 081601 (2002): gr-qc/0204094, Phys. Rev. D66, 046007 (2002): hep-th/0205111.
7. Y. Fujii, Prog. Theor. Phys. 99, 599 (1998).
8. Y. Fujii and K. Maeda, The scalar-tensor theory of gravitation, Cambridge University Press, (2003).
9. S.M. Carroll, Phys. Rev. Lett. 81, 3067 (1998): astro-ph/9806099; T. Chiba, Phys. Rev. D60, 083508 (1999): gr-qc/9903094; N. Bartolo and M. Pietroni, Phys. Rev. D61, 203518 (2000); hep-ph/9908521.
10. G. ’tHooft and M. Veltman, Nucl. Phys. B44, 189 (1972); Y. Fujii and K. Mima, Prog. Theor. Phys. 58, 991 (1977).
11. Y. Fujii, Nature Phys. Sci. 234, 5 (1971), Phys. Rev. D9, 874 (1974).
12. B. DeWitt, Dynamical theory of groups and fields, in Relativity, groups and topology, Gordon and Breach, New York, 1963. See page 787.
13. H. Matsumoto and S. Sakamoto, Prog. Theor. Phys. 105, 573 (2001).
14. B. DeWitt, Phys. Rev. 162, 1195 (1967); G. ’tHooft, Nucl. Phys. B62, 444 (1973).
15. S. Weinberg, Rev. Mod. Phys. 61, 1 (1989).
16. Y. Fujii, Prog. Theor. Phys. 26, 391 (1961).


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# Charge Ordering Due to Magnetic Symmetry Breaking

Present address: \] Institute for Solid State Physics, University of Tokyo, Kashiwanoha 5-1-5, Kashiwa 277-8531, Japan

## Abstract

It is argued that both transitions observed in 50%-doped manganites, at the Néel temperature ($`T_\mathrm{N}`$) and the so-called charge ordering temperature ($`T_{\mathrm{CO}}`$), are magnetic. $`T_\mathrm{N}`$ corresponds to the order-disorder transition, which takes place between ferromagnetic zigzag chains, while the coherent motion of spins within the chains is destroyed only around $`T_{\mathrm{CO}}`$. The magnetic structure realized below $`T_{\mathrm{CO}}`$ is highly anisotropic. It is dressed by the lattice distortion and leads to huge anisotropy of the electronic structure, which explains stability of this state as well as the form of charge-orbital pattern above $`T_\mathrm{N}`$. The type of phase transition at $`T_\mathrm{N}`$ depends on lattice interactions.

The so-called ”charge-ordered” state of the colossal magnetoresistive perovskite manganites is one of the most interesting, important, and at the same time – somewhat obscured phenomena Tokura . Since the charge ordering (CO) is accompanied by the orbital ordering (OO), and sometimes – by the very peculiar zigzag antiferromagnetic (AFM) ordering (Fig. 1), it always causes a problem with the identification of the true order parameter responsible for the physics of this complicated phase. Despite the long history, a visible progress in this direction has been made only recently Hotta ; PRL99 ; PRB01 ; Brink ; Yunoki . It appeared that many low-temperature ($`T`$) properties of CO manganites, like Nd1-xCaxMnO3 (NCMO), Nd1-xSrxMnO3 (NSMO), and La1-xSr1+xMnO4 (LSMO) at $`x`$$`=`$$`0.5`$, can be understood on the basis of purely magnetic considerations, by combining traditional ideas of the double exchange (DE) deGennes  with the anisotropy of transfer interactions between two $`e_g`$ orbitals Brink2 , and formally without involving additional mechanisms of the CO and OO.

It is true that in order to stabilize the zigzag AFM state, one should first break the cubic symmetry. Most of attempts were devoted to the search of some external (with respect to the DE) mechanism, which would first stabilize the CO/OO pattern shown in Fig. 1, and thereby predetermine the form of the zigzag AFM state. The main idea proposed in Refs. PRL99 ; PRB01  was that in the degenerate DE model, the cubic symmetry can be broken by internal means, by imposing the zigzag AFM order which forms the desired CO/OO ordering pattern, and this symmetry breaking is already sufficient to stabilize the zigzag AFM state. Thus, the appearance of the CO phase at $`T`$$`=`$$`0`$ can be explained by the following formula: anisotropic AFM order $``$ symmetry breaking $``$ stability of this AFM order. The last step is considerably facilitated by the fact that the zigzag AFM phase is a band insulator Hotta ; PRL99 ; PRB01 ; Brink . The finding is very important, because the magnetic origin of the CO phase naturally explains the fact that it can be melted by the magnetic field, giving rise to negative colossal magnetoresistance (CMR) effect melting . The second mechanism, which additionally stabilizes the zigzag AFM state PRB01 ; Yunoki , is the Jahn-Teller (JT) effect Millis .

Is this the end of the story? Apparently not, because this picture is believed to be at odds with the temperature behavior of CO manganites, which can be of two types. The first one, realized in NCMO and LSMO, is characterized by the distinct transition temperature, $`T_{\mathrm{CO}}`$, which is manifested in appearance of the CO/OO superlattice spots in the neutron Sternlieb  and x-ray Murakami  experiments, as well as the sharp increase of the resistivity, and the peak of magnetic susceptibility Tokura ; Tomioka . The Néel temperature, $`T_\mathrm{N}`$, is mainly manifested in the appearance of AFM superlattice spots Sternlieb ; Murakami . The typical values of $`T_{\mathrm{CO}}`$ and $`T_\mathrm{N}`$, observed in LSMO, are 217 and 110 K, respectively. Since $`T_{\mathrm{CO}}`$$`>`$$`T_\mathrm{N}`$, the CO is typically regarded as a more fundamental effect, which drives the AFM transition at $`T_\mathrm{N}`$. Another possibility, realized in NSMO, is the first-order transition to the metallic ferromagnetic (FM) phase above $`T_\mathrm{N}`$, which coincides with $`T_{\mathrm{CO}}`$. More generally, $`x`$$`=`$$`0.5`$ is the point of multi-critical behavior of CMR manganites Tomioka .

The purpose of this Letter is to argue that such a temperature behavior can be understood in terms of the partial spin disorder. Namely, only the long-range AFM order in the $`x`$-direction disappears at $`T_\mathrm{N}`$, whereas the FM coupling within the chains survives this transition. Thus, in the interval $`T_\mathrm{N}`$$`<`$$`T`$$`<`$$`T_{\mathrm{CO}}`$ we deal with the one-dimensional spin disorder in the direction perpendicular to the chains. The disorder is highly anisotropic. It breaks the cubic symmetry, stabilizes the FM chains and gives rise to the CO/OO pattern even above $`T_\mathrm{N}`$ Sternlieb ; Murakami . We will concentrate on the dynamics of two-dimensional pattern shown in Fig. 1.

The behavior of CO manganites at $`T`$$`=`$$`0`$ is well described by the following model, combining DE physics with the harmonic JT effect Yunoki :

$$\widehat{}_{\mathrm{𝐢𝐣}}=\xi _{\mathrm{𝐢𝐣}}\widehat{t}_{\mathrm{𝐢𝐣}}+\left(\widehat{\mathrm{\Delta }}_𝐢\delta _{\mathrm{JT}}+\frac{\kappa }{2}\delta _{\mathrm{JT}}^2J^S\zeta _𝐢\right)\delta _{\mathrm{𝐢𝐣}},$$
(1)
where $`\xi _{\mathrm{𝐢𝐣}}`$$`=`$$`\left(\frac{1+𝐞_𝐢𝐞_𝐣}{2}\right)^{1/2}`$ comment.2 . $`𝐞_𝐢`$ is the spin direction at the site $`𝐢`$. $`\widehat{t}_{\mathrm{𝐢𝐣}}`$$`=`$$`t_{\mathrm{𝐢𝐣}}^{LL^{}}`$ is the matrix of transfer interactions between nearest-neighbor (NN) $`e_g`$ orbitals: $`x^2`$-$`y^2`$ ($`L,L^{}`$$`=`$$`1`$) and $`3z^2`$-$`r^2`$ ($`L,L^{}`$$`=`$$`2`$), in the local frame specified by the oxygen sites (corresponding to the $`xy`$ and $`3z^2`$-$`r^2`$ orbitals in the $`xy`$-frame in Fig. 1). The NN hoppings along the $`(\pm 1,1)`$ directions are parameterized according to Slater and Koster: $`\widehat{t}_{\mathrm{𝐢𝐣}}`$$`=`$$`\frac{t}{4}(2`$$``$$`\sqrt{3}\widehat{\sigma }_z`$$`+\widehat{\sigma }_z)`$, where $`\widehat{\sigma }_x`$ and $`\widehat{\sigma }_z`$ are the Pauli matrices. $`\widehat{\mathrm{\Delta }}_𝐢`$$`=`$$`\mathrm{\Delta }_𝐢^{LL^{}}`$ describes the $`e_g`$ levels splitting caused by the cooperative JT distortion $`\delta _{\mathrm{JT}}`$$`=`$$`(d_L`$$``$$`d_S)/(d_L`$$`+`$$`d_S)`$: $`\widehat{\mathrm{\Delta }}_A`$$`=`$$``$$`\frac{\lambda }{2}(\sqrt{3}\widehat{\sigma }_x`$$`+`$$`\widehat{\sigma }_z)`$, $`\widehat{\mathrm{\Delta }}_A^{}`$$`=`$$`\frac{\lambda }{2}(\sqrt{3}\widehat{\sigma }_x`$$``$$`\widehat{\sigma }_z)`$, and $`\widehat{\mathrm{\Delta }}_B`$$`=`$$``$$`\frac{\lambda }{2}\widehat{\sigma }_z`$ ($`\lambda `$ being the electron-phonon coupling constant). The considered distortion is compatible with the magnetic zigzag structure (Fig. 1). $`t(\delta _{\mathrm{JT}})`$ and $`\lambda `$ are estimated from Harrison’s law for the $`p`$-$`d`$ transfer interactions PRB01 . This yields $`\lambda `$$``$$`14t_0`$. $`J^S`$$`<`$$`0`$ is the AFM superexchange (SE) coupling between NN spins ($`|J^S|`$$``$$`0.1t_0`$ Springer ) and $`2\zeta _𝐢`$$`=`$$`_{𝐧\mathrm{NN}}𝐞_𝐢𝐞_𝐧`$. The spring constant $`\kappa `$ may vary from several tens to hundreds eV Millis  (below we will give a more realistic estimate for $`\kappa `$ from the analysis of the phase transition at $`T_\mathrm{N}`$). $`t_0`$$`=`$$`t(0)`$ is used as the energy unit ($`t_0`$$`=`$$`0.7`$ eV Springer ).

What goes first in the Hamiltonian (1) and causes the required anisotropy of the electronic structure: the magnetism or the JT effect? In the harmonic approximation around a homogeneous magnetic state, the ground state may have only one minimum at $`\delta _{\mathrm{JT}}`$$`=`$$`0`$ LAZ . Therefore, the JT distortion alone cannot be the source of the anisotropy. On the other hand, the magnetic part of the Hamiltonian (1) can, and the equilibrium magnetic structure at $`T`$$`=`$$`0`$ can be successfully described in terms of competition between DE and SE interactions Hotta ; PRL99 ; PRB01 ; Brink . Therefore, even for the finite-temperature description, it seems to be logical to start with purely magnetic Hamiltonian by enforcing $`\delta _{\mathrm{JT}}`$$`=`$$`0`$ in Eq. (1). What do we expect in this case?

The stability condition of the zigzag AFM phase at $`T`$$`=`$$`0`$ is given by $`J_{AB}^{}`$$`<`$$`|J^S|`$$`<`$$`J_{AB}^{}`$, where $`J_{AB}^{}`$ ($`J_{AB}^{}`$) are the NN DE interactions within the same (between different) zigzag chains PRB01 . For $`\delta _{\mathrm{JT}}`$$`=`$$`0`$ the exchange anisotropy $`\mathrm{\Delta }J`$$`=`$$`J_{AB}^{}`$$``$$`J_{AB}^{}`$ is of the order of $`0.07`$ (and becomes larger for $`\delta _{\mathrm{JT}}`$$`>`$$`0`$). Our basic idea is to connect this anisotropy, which roughly corresponds to the temperature range of 550 K, with the existence of two transition points, $`T_\mathrm{N}`$ and $`T_{\mathrm{CO}}`$. Since $`|J^S|`$ is close to $`J_{AB}^{}`$ (about $`0.106`$ for $`\delta _{\mathrm{JT}}`$$`=`$$`0`$), the AFM coupling between the chains, $`J_{AB}^{}`$$`+`$$`J^S`$, will be much weaker than the FM interaction within the chain, $`J_{AB}^{}`$$`+`$$`J^S`$. Therefore, the long-range AFM order in the $`x`$-direction will be destroyed first with the increase of $`T`$. This corresponds to the first transition point, $`T_\mathrm{N}`$, and yields the following model for the spin disorder below $`T_\mathrm{N}`$.

All spins in an arbitrary chain $`\mathrm{}`$ are rigidly coupled by $`J_{AB}^{}`$ (the effect of inter-chain disorder on $`J_{AB}^{}`$ will be discussed below). This imposes the constraint on the spin directions within the chains: $`𝐞_𝐢\mathrm{}`$$`=`$$`𝐞_{\mathrm{}}`$. The distribution function for $`𝐞_{\mathrm{}}`$$`=`$$`(e_{\mathrm{}}^x,e_{\mathrm{}}^y,e_{\mathrm{}}^z)`$, which is required in order to calculate the thermal (or orientational) averages, can be taken in the form $`P(𝐞_{\mathrm{}})`$$``$$`\mathrm{exp}(he_{\mathrm{}}^z)`$, corresponding to the mean-field approximation for inter-chain interactions. Then, $`\xi _{\mathrm{𝐢𝐣}}`$$`=`$$`1`$ for $`𝐢`$ and $`𝐣`$ belonging to the same chain. Our goal is to calculate the electronic Green function $`\widehat{\overline{𝒢}}`$ (corresponding to the first two terms in $`\widehat{}_{\mathrm{𝐢𝐣}}`$), averaged over $`\{𝐞_{\mathrm{}}\}`$. As the zeroth order approximation along this line, all $`\xi _{\mathrm{𝐢𝐣}}`$ connecting neighboring zigzag chains are replaced by their orientational averages, $`\xi _{\mathrm{}\mathrm{}\pm 1}`$$``$$`\overline{\xi }`$ deGennes . Corrections to this approximations can be constructed in a systematic way by using the perturbation theory expansion with respect to fluctuations $`\mathrm{\Delta }\xi `$$`=`$$`\xi _{\mathrm{}\mathrm{}\pm 1}`$$``$$`\overline{\xi }`$ with subsequent averaging over $`\{𝐞_{\mathrm{}}\}`$. Then, $`\widehat{\overline{𝒢}}`$ has the following form, after transformation to the reciprocal space ($`k_y`$) along $`y`$ and using matrix representation for the orbital, chain, and inequivalent atomic indices: $`\widehat{\overline{𝒢}}_{k_y}(\epsilon )`$$`=`$$`\left\{1+_{n=2}^{\mathrm{}}\overline{(\mathrm{\Delta }\xi )^n}[\widehat{𝒢}_{k_y}^0(\epsilon )\widehat{t}_{k_y}^\pm ]^n\right\}\widehat{𝒢}_{k_y}^0(\epsilon )`$, where $`\widehat{𝒢}_{k_y}^0`$ corresponds to the zeroth order DE Hamiltonian, and $`\widehat{t}_{k_y}^\pm `$$``$$`\delta _{\mathrm{}\mathrm{}\pm 1}`$ is the super-matrix of transfer interactions between NN chains. In these (shorthanded) notations, $`\mathrm{\Delta }\xi `$’s have the same chain indices as $`\widehat{t}_{k_y}^\pm `$’s. Since $`\overline{\mathrm{\Delta }\xi }`$$`=`$$`0`$, the first-order correction vanishes, and the matrices $`\widehat{t}_{k_y}^\pm `$, which enters the matrix multiplication for higher $`n`$, should have at least one common chain index in order to contribute to $`\widehat{\overline{𝒢}}`$. Then, it is feasible to go up to $`n`$$`=`$$`2`$ and $`3`$. In most cases, $`n`$$`=`$$`2`$ is already sufficient comment.4 . Finally, $`\widehat{\overline{𝒢}}_{k_y}(\epsilon )`$ can be transformed to the real space $`\widehat{\overline{𝒢}}_{\mathrm{𝐢𝐣}}(\epsilon )`$.

The free energy $``$ is estimated using variational mean-field approach deGennes . First, we calculate the DE energy:

$$E_{\mathrm{DE}}=\frac{1}{\pi }\mathrm{Im}\underset{𝐢}{}𝑑\epsilon \mathrm{ln}\left[1+\mathrm{exp}\left(\frac{\epsilon \epsilon _F}{k_BT}\right)\right]\mathrm{Tr}_L\widehat{\overline{𝒢}}_{\mathrm{𝐢𝐢}}(\epsilon ).$$

with $`𝐢`$ running over the unit cell shown in Fig. 1, $`\epsilon _F`$ being the chemical potential, and $`\mathrm{Tr}_L`$ denoting the trace over $`L`$. Then, $`E_{\mathrm{DE}}`$ is combined with the SE energy and the entropy term, corresponding to the molecular field $`h`$ deGennes . This yields $`(h)`$, which should be minimized with respect to $`h`$ or the AFM order parameter $`m_A`$$`=`$$`\mathrm{tanh}^1h`$$``$$`h^1`$.

The orbital polarization at the site $`A`$ (the difference of atomic populations of the $`3x^2`$-$`r^2`$ and $`y^2`$-$`z^2`$ orbitals, in the oxygen frame) is given by

$$𝒪_A=\frac{1}{2\pi }\mathrm{Im}𝑑\epsilon f_T(\epsilon \epsilon _F)\mathrm{Tr}_L\{(\sqrt{3}\widehat{\sigma }_x+\widehat{\sigma }_z)\widehat{\overline{𝒢}}_{AA}(\epsilon )\},$$

where $`f_T(\epsilon \epsilon _F)`$ is the Fermi distribution function. (Similar parameter $`𝒪_B`$ related with $`\widehat{\mathrm{\Delta }}_B`$ at the site $`B`$ is of the order of $`0.1`$, and only weakly depends on the degrees of the JT distortion and the spin disorder). The charge disproportionation

$$𝒞=\frac{1}{\pi }\mathrm{Im}𝑑\epsilon f_T(\epsilon \epsilon _F)\mathrm{Tr}_L\{\widehat{\overline{𝒢}}_{AA}(\epsilon )\widehat{\overline{𝒢}}_{BB}(\epsilon )\}$$

shows the degree of CO. The stiffness of the FM zigzag chain is controlled by Springer

$$J_{AB}^{}=\frac{1}{2\pi }\mathrm{Im}𝑑\epsilon f_T(\epsilon \epsilon _F)\mathrm{Tr}_L\{\widehat{t}_{AB}\widehat{\overline{𝒢}}_{BA}(\epsilon )\}.$$

In order to be stable against the thermal fluctuations $`J_{AB}^{}`$ should satisfy the inequality: $`(J_{AB}^{}`$$`+`$$`J^S)`$$``$$`k_BT`$.

Results for $`\delta _{\mathrm{JT}}`$$`=`$$`0`$ are summarized in Fig. 2. The ordered AFM state is a band insulator Hotta ; PRL99 ; PRB01 ; Brink . Will it be insulating in the case of the spin disorder between the chains? In the zeroth order of $`\mathrm{\Delta }\xi `$, it is equivalent to the change of $`\xi _{\mathrm{}\mathrm{}\pm 1}`$ in the DE Hamiltonian from $`\overline{\xi }`$$`=`$$`0`$ ($`m_A`$$`=`$$`1`$) to $`\overline{\xi }`$$`=`$$`\frac{2}{3}`$ ($`m_A`$$`=`$$`0`$) deGennes . The corresponding electronic structure is semi-metallic (SM), meaning that there is a direct gap in each $`𝐤`$-point of the Brillouin zone. However, a finite overlap between different $`𝐤`$-points closes the real gap. Thus, the DE mechanism alone is insufficient to make the disordered zigzag phase a band insulator, though the situation is certainly close to it, and as we will see below the insulating behavior can be easily produced by the JT distortion.

The SM character of the electronic structure predetermines the type of the phase transition at $`T_\mathrm{N}`$. The collapse of the band gap at small $`m_A`$ leads to the gain of the DE energy and stabilizes an additional minimum of $``$ at $`m_A`$$`=`$$`0`$, which coexists with another minimum corresponding to an insulating phase at finite $`m_A`$. Thus, the phase transition will be of the first order, which is characterized by the abrupt change of $`𝒪_A`$. $`𝒞`$ vanishes without distortion PRB01 . This scenario is qualitatively consistent with the behavior of NSMO compounds. It also explains the observed phase coexistence around $`T_\mathrm{N}`$ Mori ; comment.1 , which may lead to the percolation and the CMR effect percolation . However, most of CO manganites, like NCMO, exhibit a continuous second-order transition at $`T_\mathrm{N}`$.

What is missing in the above picture? Below, we will argue that the difference between NSMO and NCMO is controlled by the ratio $`\lambda /\kappa `$ Yunoki , and can be understood by considering the response of the crystal structure to the highly anisotropic magnetic structure. First, we estimate the force $`f`$$`=`$$``$$`E_{\mathrm{DE}}/\delta _{\mathrm{JT}}|_{\delta _{\mathrm{JT}}=0}`$ acting on the lattice degrees of freedom and coming from the electron-phonon term in Eq. (1comment.3 , which couples $`\delta _{\mathrm{JT}}`$ with the parameters of orbital polarization. This yields (per one unit cell) $`f`$$`=`$$``$$`2\lambda (𝒪_A`$$`+`$$`𝒪_B)`$, which is of the order of 10 eV. Then, we note that even a modest distortion $`\delta _{\mathrm{JT}}`$$``$$`0.04`$ comment.5  is sufficient to open the band gap in the disordered zigzag phase (Fig. 3). Using $`f`$, we estimate the spring constant $`\kappa `$ which would correspond to such equilibrium distortion: $`\kappa `$$`=`$$``$$`f/4\delta _{\mathrm{JT}}`$. This yields $`\kappa `$$``$$`65`$ eV, in agreement previous estimates Millis . The temperature behavior corresponding to this ratio $`\lambda /\kappa `$ is shown in Fig. 3c. Since the system is insulating for all $`m_A`$, $`(m_A)`$ has only one minimum for each $`T`$. Therefore, the transition at $`T_\mathrm{N}`$ will be of the second order. Finite $`\delta _{\mathrm{JT}}`$ enhanced the orbital polarization $`𝒪_A`$ and gives rise to the small charge disproportionation $`𝒞`$. Both parameters are affected by the spin disorder and monotonously decrease with $`T`$, that explains similar intensity change of the CO/OO superlattice peaks in the neutron scattering experiment Sternlieb . $`T_\mathrm{N}`$, obtained from $`^2/m_A^2|_{m_A=0}`$$`=`$$`0`$, depends on the JT distortion. For $`\delta _{\mathrm{JT}}`$$`=`$$`0.04`$ and $`|J^S|`$$`=`$$`0.09`$, it is of the order of $`120`$ K, which is close to the experimental value $`110`$ K observed in LSMO Tokura ; Sternlieb . Then, the ration is $`(J_{AB}^{}`$$`+`$$`J^S)/k_BT_\mathrm{N}`$ is about 4, meaning that the FM coupling within the chains remains robust even around $`T_\mathrm{N}`$. This justifies the proposed model of inter-chain disorder.

In summary, CO in manganites is a magnetic phenomenon. The transition from the AFM ground state to the paramagnetic state goes through the intermediate phase, in which the FM order within the zigzag chains coexists with the inter-chain disorder. This implies that the multi-critical behavior in CMR manganites Tomioka  is the result of competition between different magnetic phases, which is only masked by spurious CO. Details of the phase transition at $`T_{\mathrm{CO}}`$ present an interesting and so far the least understood part of the problem. We would like to stress two points. (i) The transition should be discontinuous, so that the change of the electronic structure should be sufficient to open the gap and self-stabilize the anisotropic magnetic state. (ii) The transition should be accompanied by the lattice distortion, which is a necessary precondition for insulating behavior above $`T_\mathrm{N}`$. Both features are clearly seen in the experiment Tokura . An interesting question, which still remains to be understood is how the FM zigzag chains will break. An important step in this direction would be the explanation of incommensurate CO superstructures observed just below $`T_{\mathrm{CO}}`$ Chen .

I thank all member of Tokura group for the great deal of inspiration by numerous experimental stories about CO in manganites.


text:
# New classes of quasi-solvable potentials,their exactly-solvable limit and related orthogonal polynomials

## 1 Introduction

In recent times elliptic potentials have proved to be an important addition \[1–3\] to the class of solvable  and quasi-solvable \[6–8\] potentials in quantum mechanics. In particular, within the sl(2,$``$) algebra,exact solutions of Lamé and associated Lamé equation have been obtained \[9–12\] for various ranges of the potential parameters. Indeed a handful of theorems relating to the properties of elliptic potentials are known for a long time \[13–16\] including the study of the properties of the corresponding wavefunctions . The solutions of associated Lamé equation have also been obtained  by using these theorems which, however, do not use the sl(2,$``$) technique. Note that some new elliptic models based on Weierstrass $`\mathrm{}`$ function have recently been proposed  wherein it is shown that the corresponding Hamiltonians possess the so-called energy-reflection symmetry .

By the term quasi-exactly solvable(QES) periodic potentials we mean potentials consisting of finite number of allowed bands and expressible as doubly-periodic elliptic functions which are either Jacobian elliptic functions $`snxsn(x,k),cnxcn(x,k),dnxdn(x,k)`$ of real elliptic modulus parameter $`k(0<k^2<1)`$ or Weierstrass $`\mathrm{}`$ function. This is in sharp contrast with the ordinary ES periodic potentials with a single period.

There is an intriguing relation between ES and QES class. In fact an sl(2) based construction with an $`n`$-dimensional finite space representation gives ($`n`$+1) levels for a Hamiltonian designated as QES model. It was pointed out in Ref. 8 that if one can construct a Hamiltonian having no explicit dependence on $`n`$, then in the limit $`n\mathrm{}`$ the ES models are recovered. This provides a sufficient reason to believe that corresponding to every ES model there ought to exist a QES model which in the proper limit goes over to the former.

In this article we show that the elliptic parameter $`k`$ can be used for passage from QES to ES in the periodic models. We derive three new QES periodic potentials involving Jacobian elliptic functions. The elliptic functions having real and imaginary period reduce to ordinary periodic functions namely hyperbolic(imaginary period) and trigonometric(real period) functions as the modulus parameter $`k`$ goes to 1 and 0. We exploit this interesting property of elliptic functions to show that our QES models are connected with some well known ES periodic class. Note that we do not intend to take the limit $`n\mathrm{}`$ and as such we cannot expect to recover the whole spectrum for ES models. Rather we show that the limit $`k1`$ and $`0`$ correctly map the few lower states of the QES and ES periodic potentials.

The plan of this article is as follows. In Sec. 2 we briefly review the basics of the sl(2,$``$) Lie-algebraic formalism and generate Type I,Type II and Type III models within this framework. The method of construction of the related orthogonal polynomials is also sketched here. Specific examples are constructed in Sec. 3 for each of them based on some real values of the potential parameters. In Sec. 4 we systematically analyze the ES-limit of our results to show how this limit can reproduce the ES results. Finally we present our conclusions in Sec. 5.

## 2 New QES potentials from sl(2,$``$) and related orthogonal polynomials

To start with, let us adopt the following differential realization of the sl(2,$``$) generators

$$T^+=\xi ^2_\xi n\xi ,T^0=\xi _\xi \frac{1}{2}n,T^{}=_\xi ,$$
(2. 1)
obeying commutation relations

$$[T^+,T^{}]=2T^0,[T^0,T^\pm ]=\pm T^\pm ,$$
(2. 2)
where $`n`$ is a non-negative integer. The gauged Hamiltonian is taken as the standard homogeneous quadratic combination of sl(2,$``$) generators along with linear terms:

$$H_G=C_{++}T^{+^2}C_{00}T^{0^2}C_{}T^^2C_+T^+C_0T^0C_{}T^{}d,$$
(2. 3)
where $`C_{ii}`$,$`C_j`$($`i,j=0,\pm `$) are numerical parameters and $`d`$ is a suitably chosen constant taken as function of $`C_j`$. Note that $`d`$ plays the role of an overall shift in the energy scale. This psudo degree of freedom allows us to obtain QES models in the desired form.

Substitution of (2.1) into (2.3) yields

$`H_G(\xi )`$ $`=`$ $`(C_{++}\xi ^4+C_{00}\xi ^2+C_{})_\xi ^2[2(1n)C_{++}\xi ^3+C_+\xi ^2+\{(1n)C_{00}`$ (2. 4)
$`+C_0\}\xi +C_{}]_\xi [n(n1)C_{++}\xi ^2nC_+\xi +{\displaystyle \frac{n^2}{4}}C_{00}{\displaystyle \frac{n}{2}}C_0+d],`$
which after a coordinate transformation

$$x(\xi )=^\xi 𝑑\tau /\sqrt{C_{++}\tau ^4+C_{00}\tau ^2+C_{}},$$
(2. 5)
converts $`H_G`$ into the form

$`H_G(x)`$ $`=`$ $`_x^2+{\displaystyle \frac{2nC_{++}\xi ^3(x)C_+\xi ^2(x)+(nC_{00}C_0)\xi (x)C_{}}{\sqrt{C_{++}\xi ^4(x)+C_{00}\xi ^2(x)+C_{}}}}_x`$ (2. 6)
$`[n(n1)C_{++}\xi ^2(x)nC_+\xi (x)+{\displaystyle \frac{n^2}{4}}C_{00}{\displaystyle \frac{n}{2}}C_0+d],`$
where $`\xi =\xi (x)`$ is determined by (2.5).

Let us now consider the Schrödinger equation with the potential $`V(x)`$

$$H(x)\psi (x)[_x^2+V(x)]\psi (x)=E\psi (x)$$
(2. 7)
Writing $`\psi (x)`$ in the form

$$\psi (x)=\mu (x)\chi (x),$$
(2. 8)
we obtain

$$H_G(x)\chi (x)[_x^22(\frac{\mu ^{^{}}}{\mu })_x(\frac{\mu ^{^{}}}{\mu })^2(\frac{\mu ^{^{}}}{\mu })^{^{}}+V]\chi (x)=E\chi (x).$$
(2. 9)
Comparing (2.6) and (2.9) we find for the potential $`V(x)`$ and the gauge factor $`\mu (x)`$ the following relationships

$$V(x)=(\frac{\mu ^{^{}}}{\mu })^2+(\frac{\mu ^{^{}}}{\mu })^{^{}}[n(n1)C_{++}\xi ^2nC_+\xi +\frac{n^2}{4}C_{00}\frac{n}{2}C_0+d],$$
(2. 10)
$$\mu (x)=[C_{++}\xi ^4+C_{00}\xi ^2+C_{}]^{\frac{n}{4}}\mathrm{exp}[^\xi \frac{C_+\tau ^2+C_0\tau +C_{}}{2(C_{++}\tau ^4+C_{00}\tau ^2+C_{})}𝑑\tau ].$$
(2. 11)
Note that the choice of numerical parameters $`C_{ii}`$ must be such that equation (2.5) may be invertible in terms of $`\xi =\xi (x)`$. For our purpose $`\xi (x)`$ needs to be expressed in terms of Jacobian elliptic functions. In Ref. 12 we gave an almost exhaustive list of the choice of $`C_{ii}`$ leading to various new classes of elliptic potentials. Here we consider the following three types of combinations of parameters namely

$`\text{Type I :}C_{++}=k^2`$ $`C_{00}=2k^21`$ $`C_{}=k^^2,`$ (2. 12)
$`\text{Type II:}C_{++}=k^2`$ $`C_{00}=(1+k^2)`$ $`C_{}=1,`$ (2. 13)
$`\text{Type III}:C_{++}=k^^2`$ $`C_{00}=1+k^^2`$ $`C_{}=1,`$ (2. 14)
where $`k^2(0,1)`$ and $`k^^2=1k^2`$. Each of the above types defines different coordinate transformations through (2.5). These give respectively $`\xi =cnx,cnx/dnx`$ and $`snx/cnx`$ for the three types mentioned above.

In this way we are then led to the following new classes of elliptic potentials:

Type I : $`V(x)=`$ $`[B^2+A(A+1)]{\displaystyle \frac{dn^2x}{sn^2x}}2B(A+{\displaystyle \frac{1}{2}}){\displaystyle \frac{cnx}{sn^2x}},x(0,2K)`$ (2. 15)
Type II: $`V(x)=`$ $`B(B+1){\displaystyle \frac{dn^2x}{sn^2x}}A(A+1)dn^2x,x(0,2K)`$ (2. 16)
$`\text{Type III}:`$ $`V(x)=`$ $`[B^2A(A+1)]k^2cn^2x+2Bk^2(A+{\displaystyle \frac{1}{2}})snxcnx,x(\mathrm{},\mathrm{})`$ (2. 17)
where $`K=_0^{\pi /2}𝑑\alpha /\sqrt{1k^2\mathrm{sin}^2\alpha }`$ is the complete elliptic integral of 1st kind. Note that in (2.15)–(2.17) the potential parameters $`A,B`$ and the choices of $`C_j`$ and the spin parameter $`n`$ in (2.10) in terms of $`A,B`$ are given in Table 1.

The constant d is chosen as

$`\text{Type I}:`$ $`d=`$ $`{\displaystyle \frac{C_0}{4}}\{C_04k^^2(n+1)\}+{\displaystyle \frac{C_+}{2k^2}}(k^2C_{}k^^2C_+)+{\displaystyle \frac{n(n+2)}{2}}k^^2`$ (2. 18)
$`\text{Type II}:`$ $`d=`$ $`({\displaystyle \frac{C_+}{2k}})^2{\displaystyle \frac{C_0}{2}}(n+1)+{\displaystyle \frac{n(n+2)}{4}}(1+k^2)`$ (2. 19)
$`\text{Type III}:`$ $`d=`$ $`{\displaystyle \frac{1}{4}}[({\displaystyle \frac{C_+}{k^{^{}}}})^2n(n+2)(2k^2)2C_0(n+1)]`$ (2. 20)
Note that while the Type III potential is defined over the entire $`x`$-axis, Type I and Type II potentials are singular at $`x=0,2K`$ and so defined over an open domain $`(0,2K)`$. It follows from the oscillation theorem that we need to find the periodic solutions \[of period $`4K`$(or $`8K`$)\] for $`4K`$-periodic potential of Type I and periodic solutions \[of period $`2K`$(or $`4K`$)\] for $`2K`$-periodic potentials of Type II and Type III at $`E=E_j`$. The monotonic increasing sequence $`\{E_j\}`$, where $`E_0<E_1E_2<E_3E_4\mathrm{},`$ gives the characteristic values of the energy parameter.

Following the analysis made in  we can find the effective combinations of the potential parameters $`A,B`$. We see that the Type I and Type III potentials are invariant under the translation $`A,BA^{^{}},B^{^{}}`$ where $`A^{^{}}=A1,B^{^{}}=B`$ and Type II potential is invariant under $`A,BA^{^{}},B^{^{}}`$ where $`A^{^{}}=A1,B^{^{}}=B1`$. Further due to the periodic relations $`sn(x+2K)=snx,cn(x+2K)=cnx,dn(x+2K)=dnx,`$ it results that the effective regions in the $`A`$-$`B`$ plane for Type I–III models are bounded by the constraints $`A1/2,B0;A,B1/2`$ and $`A1/2,B`$ respectively. It may be pointed out that the eigenstates and spectra of Type I potential for $`B<0`$ can be obtained from those for $`B>0`$ under the coordinate translation $`xx+2K`$.

Before concluding this section let us briefly describe the method of construction of families of orthogonal polynomials  generated by the eigenstates of a QES Hamiltonian. Let us consider a gauged eigenvalue equation

$$H_G(\xi )\chi (\xi )=E\chi (\xi )$$
(2. 21)
where we identify $`\chi (\xi (x))\chi (x)`$ as given in (2.8). We now expand the gauged eigenfunction $`\chi (\xi )`$ in the form

$$\chi (\xi )=(\frac{\xi _2\xi }{\xi _1\xi _2})^n\underset{j=0}{\overset{\mathrm{}}{}}\frac{P_j(E)}{j!}(\frac{\xi _1\xi }{\xi _2\xi })^j$$
(2. 22)
where $`\xi _1,\xi _2`$ are two distinct roots of the coeffecient of $`_\xi ^2`$ in (2.4). Now a suitable choice of $`\xi _1,\xi _2`$ (note that $`\xi _1,\xi _2`$ can be chosen in six ways) gives us a three-term recursion relation satisfied by {$`P_j(E)`$}

$`[(2jn+1)\widehat{C}_0+\widehat{C}_{}]P_{j+1}`$ $`=`$ $`[E+d_1+\widehat{C}_0(j{\displaystyle \frac{n}{2}})+\widehat{C}_{00}(j{\displaystyle \frac{n}{2}})^2]P_j`$ (2. 23)
$`+j(j1n)[(2jn1)\widehat{C}_{+0}+\widehat{C}_+]P_{j1},`$
$`(j0),`$
where $`\widehat{C}_{ij}`$ are determined from the relations

$`\widehat{C}_{+0}`$ $`=`$ $`{\displaystyle \frac{1}{(\xi _1\xi _2)^2}}[2\xi _1\xi _2^3C_{++}+\xi _2(\xi _1+\xi _2)C_{00}+2C_{}],`$
$`\widehat{C}_{00}`$ $`=`$ $`{\displaystyle \frac{1}{(\xi _1\xi _2)^2}}[6\xi _1^2\xi _2^2C_{++}+(\xi _1^2+\xi _2^2+4\xi _1\xi _2)C_{00}+6C_{}],`$
$`\widehat{C}_0`$ $`=`$ $`{\displaystyle \frac{1}{(\xi _1\xi _2)^2}}[2\xi _1^3\xi _2C_{++}+\xi _1(\xi _1+\xi _2)C_{00}+2C_{}],`$ (2. 24)
and $`\widehat{C}_j,d_1`$ are given by

$`\widehat{C}_+`$ $`=`$ $`{\displaystyle \frac{1}{\xi _1\xi _2}}[\xi _2^2C_++\xi _2C_0+C_{}],`$
$`\widehat{C}_0`$ $`=`$ $`{\displaystyle \frac{1}{\xi _1\xi _2}}[2\xi _1\xi _2C_++(\xi _1+\xi _2)C_0+2C_{}],`$
$`\widehat{C}_{}`$ $`=`$ $`{\displaystyle \frac{1}{\xi _1\xi _2}}[\xi _1^2C_++\xi _1C_0+C_{}],`$
$`d_1`$ $`=`$ $`d+{\displaystyle \frac{n(n+2)}{12}}(C_{00}\widehat{C_{00}}).`$ (2. 25)
From equation (2.23)–(2.25) it transpires that the eigenstates of Type I–III Hamiltonians generate,in general, different orthogonal family of polynomials in the energy variable corresponding to each algebraization of Table 1 provided

$$(2jn+1)\widehat{C}_0+\widehat{C}_{}0,j0$$
(2. 26)
The family {$`P_j`$(E)} can be expressed in terms of monic polynomials {$`\stackrel{~}{P}_j`$(E)} satisfying the recurrence relation

$`\stackrel{~}{P}_{j+1}`$ $`=`$ $`(E\lambda _j)\stackrel{~}{P}_j\rho _j\stackrel{~}{P}_{j1},`$ (2. 27)
$`\stackrel{~}{P}_j`$ $`=`$ $`\omega _jP_j,j0,`$ (2. 28)
where $`\stackrel{~}{P}_1=P_10`$ and $`\stackrel{~}{P}_0=P_01`$. It is now straightforward to write down the expression of eigenfunctions from (2.8) and (2.22). It follows from equation (2.23) that $`\rho _0=0`$ and $`\rho _{n+1}=0`$; so the infinite power series expansion in (2.22) truncates after the ($`n`$+1)-th term since the coeffecients $`P_j(E_i)`$ vanishes for $`j>n`$, where $`E_i(i=0,1,\mathrm{},n)`$ are the zeros of the critical polynomial $`\stackrel{~}{P}_{n+1}(E)`$. This points to the fact that Type I–Type III potentials belong to QES class having $`(n+1)`$ levels for each algebraization. The final expression of the band-edge eigenfunctions may be written in the form

$$\psi _{E_i}(x)=\mu (x)(\xi (x)\xi _2)^n\underset{j=0}{\overset{n}{}}\frac{P_j(E_i)}{j!}(\frac{\xi (x)\xi _1}{\xi (x)\xi _2})^j,(i=0,1,\mathrm{},n),$$
(2. 29)
where $`\mu (x)`$ is determined from (2.11) for each of the three types given by (2.12)–(2.14) and the band-edge eigenvalues are $`E_0,E_1,\mathrm{}E_n`$. Note that $`n`$ is to be computed for each of the algebraization in Table 1.

## 3 Eigenstates and spectra of Type I–III models for some real values of the potential parameters

In this section we construct some examples based upon the general results obtained in the previous section. It may be useful to collect the following identities and differential relations among the Jacobian elliptic functions which will be frequently used:

$$sn^2x+cn^2x=1,dn^2x+k^2sn^2x=1$$

$$sn^{^{}}x=cnxdnx,cn^{^{}}x=snxdnx,dn^{^{}}x=k^2snxcnx$$

In the following examples we denote the eigenstates\[spectra\] by $`\varphi _r(x)[e_r]`$ whenever ordering is possible. Otherwise we denote them by $`\psi _{E_i}[E_i]`$ and $`\psi _{E_i^{^{}}}[E_i^{^{}}]`$ indicating different algebraizations.

### 3.1 Type I model \[defined on the domain (0,2K)\]

We have got six algebraizations (see the solution 1.1–1.6 of Table 1) for Type I Hamiltonian (2.15). For each of them the corresponding eigenstates generate an orthogonal family of polynomials satisfying the recurrence relation (2.27). The explicit expressions of $`\rho _j`$ and $`\lambda _j`$ corresponding to each solutions of $`n`$ are given in Table 2. The corresponding expressions of $`\omega _j`$ together with the choice of $`\xi _1,\xi _2`$ and the overall restrictions on potential parameters are given in Table 3.

It is clear that the algebraic solutions are obtained for the following two cases:

$$\text{Case 1.}A(1)(\frac{1}{2}),B$$

Here $`B`$ is any real parameter and for each real values of $`B`$, $`A`$ is allowed to take $`0,1/2,1,3/2,\mathrm{},\mathrm{\Lambda }B`$($`\mathrm{\Lambda }`$ is an integer or half-integer). For integer values of $`A`$, from the algebraizations 1.1–1.2 we get $`(2A+1)`$ band edge eigenstates and eigenvalues. Also for half-integer values of $`A`$ the algebraization 1.4 gives $`(A+1/2)`$ solutions of the Schrödinger equation.

$$\text{Case 2.}B\frac{1}{2},A$$

Here $`A`$ is any real number and $`B`$ is allowed to take values $`1/2,1,3/2,\mathrm{},\mathrm{\Lambda }A+1`$($`\mathrm{\Lambda }`$ is integer or half-integer). It is to be noted that algebraization 1.3 is considered for integer values of $`B`$ and 1.5–1.6 for half-integer $`B`$.

We now consider some specific examples when both of $`A`$ and $`B`$ are integer or half-integer.

$$\text{1. A = 0,B=1/2 :}V(x)=\frac{1}{4}\frac{dn^2x}{sn^2x}\frac{1}{2}\frac{cnx}{sn^2x}$$

$$\varphi _0(x)=\sqrt{\frac{snx}{1+cnx}},e_0=\mathrm{\hspace{0.17em}0}$$
(3. 1)
$$\text{2. A=0,B=3/2 :}V(x)=\frac{9}{4}\frac{dn^2x}{sn^2x}\frac{3}{2}\frac{cnx}{sn^2x}$$

$$\varphi _0(x)=(\frac{snx}{1+cnx})^{3/2},e_0=\mathrm{\hspace{0.17em}0}$$
(3. 2)
$$\text{3. A = 1/2,B=1 :}V(x)=\frac{7}{4}\frac{dn^2x}{sn^2x}2\frac{cnx}{sn^2x}$$

$$\varphi _0(x)=\frac{\sqrt{snxdnx}}{1+cnx}exp(\frac{i}{2}tan^1\frac{kcnx}{k^{^{}}}),e_0=\frac{12k^2}{4}ikk^{^{}}$$
(3. 3)
$$\text{4. A=1/2,B=2 :}V(x)=\frac{19}{4}\frac{dn^2x}{sn^2x}4\frac{cnx}{sn^2x}$$

$$\varphi _0(x)=\frac{\sqrt{dnx}sn^{3/2}x}{(1+cnx)^2}exp(\frac{i}{2}tan^1\frac{kcnx}{k^{^{}}}),e_0=\frac{12k^2}{4}2ikk^{^{}}$$
(3. 4)
$$\text{5. A = 1,B=3/2 :}V(x)=\frac{17}{4}\frac{dn^2x}{sn^2x}\frac{9}{2}\frac{cnx}{sn^2x}$$

For $`0<k^2<\mathrm{\hspace{0.17em}1}/2`$,

$$\varphi _{0,1}(x)=\frac{\sqrt{snx}}{(1+cnx)^{5/2}}[g_{}(k)cn^2x+4cnx+4g_{}(k)],e_{0,1}=14k^2+\frac{1}{2}g_{}(k),$$
(3. 5)
$$\varphi _2(x)=\frac{dnx\sqrt{snx}}{(1+cnx)^{3/2}},e_2=12k^2,$$
(3. 6)
$$\text{where}g_\pm (k)=\mathrm{\hspace{0.17em}6}k^21\pm \sqrt{136k^2k^^2}$$

For $`1/2<k^2<\mathrm{\hspace{0.17em}1}`$,the suffixes 0,1,2 have to be replaced by 1,2,0 respectively.

Proceeding in the same fashion,we can find the eigenstates and spectra for higher values of A and B.

### 3.2 Type II model \[defined on the domain (0,2K)\]

Here two algebraizations are obtained (see the solution 2.1–2.2 of Table 1). The related orthogonal polynomials are determined by the entries 2.1–2.2 of Table 4 and Table 5.

Note that both algebraizations are valid provided $`A`$ is restricted to positive half-integer values only while the other parameter $`B`$ is arbitrary.

Some examples are furnished below.

$$\mathrm{𝟏}.𝐀=\frac{\mathrm{𝟏}}{\mathrm{𝟐}}:V(x)=B(B+1)\frac{dn^2x}{sn^2x}\frac{3}{4}dn^2x$$
(3. 7)
$$\varphi _0(x)=\frac{sn^{B+1}x}{(cnx+dnx)^{B+1/2}},e_0=\frac{k^^2}{2}\frac{k^2}{4}(2B+1)^2$$

For $`B\mathrm{\hspace{0.17em}0}`$, the following degenerated state is found:

$$\psi _0(x)=(cnx+dnx)^{B+1/2}/sn^Bx$$

$$\mathrm{𝟐}.𝐀=\frac{\mathrm{𝟑}}{\mathrm{𝟐}}:V(x)=B(B+1)\frac{dn^2x}{sn^2x}\frac{15}{4}dn^2x$$
(3. 8)
$`\varphi _{0,1}(x)`$ $`=`$ $`{\displaystyle \frac{sn^{B+1}x}{(cnx+dnx)^{B+3/2}}}[\{(1+k^2)(B+{\displaystyle \frac{3}{2}})+\eta _{}(k)\}cn^2x`$
$`+2(B+{\displaystyle \frac{3}{2}})cnxdnx+k^^2(B+{\displaystyle \frac{3}{2}})\eta _{}(k)],`$
$$e_{0,1}=\frac{6k^210k^2(2B+1)^2}{4}\sqrt{2(1+k^4)(B+\frac{1}{2})^2k^^4},$$

$$\text{where}\eta _\pm (k)=(1+k^2)(B+\frac{1}{2})\pm \sqrt{2(1+k^4)(B+\frac{1}{2})^2k^^4}$$

For $`B\mathrm{\hspace{0.17em}0}`$ two other degenerated states are obtained:

$`\psi _{0,1}(x)`$ $`=`$ $`{\displaystyle \frac{(cnx+dnx)^{B1/2}}{sn^Bx}}[\{(1+k^2)(B+{\displaystyle \frac{3}{2}})+\eta _{}(k)\}cn^2x`$
$`+(12B)cnxdnxk^^2(B{\displaystyle \frac{1}{2}})(1+k^2)(2B+1)\eta _{}(k)]`$
### 3.3 Type III model \[defined on the entire real line\]

This corresponds to three algebraizations (see the solution 3.1–3.3 of Table 1), the first two of which are for an integer $`A`$ while the third one is for an half-integer $`A`$. As before, the eigenstates generate an orthogonal family of polynomials in the energy variable for each algebraization.

The recurrence relation (2.27) is determined by the entries 3.1–3.3 of Table 4 and Table 5. The other parameter $`B`$ takes arbitrary values.

We now consider some examples.

$$\mathrm{𝟏}.𝐀=\mathbf{\hspace{0.17em}0}:V(x)=B^2k^2cn^2x+Bk^2snxcnx$$
(3. 9)
$$\varphi _0(x)=exp(Btan^1\frac{snx}{cnx}),e_0=B^2k^^2$$

$$\mathrm{𝟐}.𝐀=\frac{\mathrm{𝟏}}{\mathrm{𝟐}}:V(x)=(B^2\frac{3}{4})k^2cn^2x+2Bk^2snxcnx$$
(3. 10)
$$\varphi _0(x)=\sqrt{dnx}exp[Btan^1(\frac{snx}{cnx})+\frac{i}{2}tan^1(\frac{k^{^{}}snx}{cnx})],e_0=\frac{k^2}{2}+(\frac{1+2Bik^{^{}}}{2})^2$$

$$\mathrm{𝟑}.𝐀=\mathbf{\hspace{0.17em}1}:V(x)=(B^22)k^2cn^2x+3Bk^2snxcnx$$
(3. 11)
$$\varphi _0(x)=dnxexp(Btan^1\frac{snx}{cnx}),e_0=B^2k^^2k^2$$

$$\varphi _{1,2}^{(i)}(x)=[(k^2\sqrt{k^416k^^2B^2})snx+4Bcnx]exp(Btan^1\frac{snx}{cnx}),$$

$$\varphi _{1,2}^{(ii)}(x)=[4Bk^^2snx+(k^2\pm \sqrt{k^416k^^2B^2})cnx]exp(Btan^1\frac{snx}{cnx}),$$

$$e_{1,2}=1\frac{3}{2}k^2B^2k^^2\frac{1}{2}\sqrt{k^416k^^2B^2},$$

where the superscripts in the eigenstates indicate their double-degeneracy.

## 4 ES-limit of QES models

We have so far constructed three new classes of QES potentials and explicitly obtained their eigenstates and spectra. Our purpose in this section is to show that corresponding to each type there is associated an ES class potential. It is useful to write down the following results of the ES-limit

$`sn(x,k)\begin{array}{c}k1\hfill \\ \hfill \\ k0\hfill \end{array}\{\begin{array}{c}\mathrm{tanh}x\hfill \\ \mathrm{sin}x\hfill \end{array},`$ $`cn(x,k)\begin{array}{c}k1\hfill \\ \hfill \\ k0\hfill \end{array}\{\begin{array}{c}\text{sech}x\hfill \\ \mathrm{cos}x\hfill \end{array},`$ $`dn(x,k)\begin{array}{c}k1\hfill \\ \hfill \\ k0\hfill \end{array}\{\begin{array}{c}\text{sech}x\hfill \\ 1\hfill \end{array}`$ (4. 16)
Each of the three types of potentials are doubly periodic, one is real and the other imaginary. As $`k1`$(or 0) we get an ES potential having an imaginary(or real) period.

### 4.1 ES classes associated to Type I model

We have already shown that the Type I model \[cf. equation (2.15)\] belongs to the QES periodic class. The potential has a real period $`4K`$ and imaginary period $`4K^{^{}}`$, where $`K^{^{}}K(k^{^{}})`$. Using the relation (4.1) and the relation

$`K[K^{^{}}]\begin{array}{c}k1\hfill \\ \hfill \\ k0\hfill \end{array}\{\begin{array}{c}\mathrm{}[\pi /2]\hfill \\ \pi /2[\mathrm{}]\hfill \end{array}`$ $`\begin{array}{c}\\ ,\hfill \end{array}`$ (4. 24)
we see that the QES model is also exactly solvable when the modulus parameter $`k1`$ and 0. The associated ES classes are given by

$$k1:V_1(x)=[B^2+A(A+1)]\text{cosech}^2x2B(A+\frac{1}{2})\text{cosech}x\mathrm{coth}x,x(0,\mathrm{})$$
(4. 25)
$$k0:V_2(x)=[B^2+A(A+1)]\text{cosec}^2x2B(A+\frac{1}{2})\text{cosec}x\mathrm{cot}x,x(0,\pi ),$$
(4. 26)
whose eigenstates and spectra are

$`\psi _r^{(1)}(x)`$ $`=`$ $`(\mathrm{cosh}x1)^{\frac{BA}{2}}(\mathrm{cosh}x+1)^{\frac{B+A}{2}}P_r^{(BA\frac{1}{2},BA\frac{1}{2})}(\mathrm{cosh}x),`$
$`\psi _r^{(2)}(x)`$ $`=`$ $`(1\mathrm{cos}x)^{\frac{BA}{2}}(1+\mathrm{cos}x)^{\frac{B+A}{2}}P_r^{(BA\frac{1}{2},BA\frac{1}{2})}(\mathrm{cos}x),`$ (4. 27)
$$E_r^{(1)}=(Ar)^2,E_r^{(2)}=(Ar)^2,(r=0,1,2,\mathrm{})$$
(4. 28)
where $`P_r^{(\alpha ,\beta )}(x)`$ is the Jacobi polynomial and the superscripts 1 and 2 indicates the potentials $`V_1(x)`$ and $`V_2(x)`$ respectively. Note that we have solved the Type I spectral problem(see Subsec. 3.1) when at least one of the parameters $`A,B`$ is an integer or an half-integer. Thus the ES results (4.5) and (4.6) can be reproduced from the associated QES results for this restricted domain of potential parameters only.

We now consider the ES-limits of the examples given in Subsec. 3.1 \[see equations (3.1)–(3.5)\]. In the following the superscripts in the eigenstates indicate whether they correspond to the potentials $`V_1(x)`$ and $`V_2(x)`$.

$$\mathrm{𝟏}.𝐀=\mathbf{\hspace{0.17em}0},𝐁=\mathrm{𝟏}/\mathrm{𝟐}:$$

$`V_1(x)`$ $`=`$ $`{\displaystyle \frac{1}{4}}\text{cosech}^2x{\displaystyle \frac{1}{2}}\text{cosech}x\mathrm{coth}x`$ (4. 29)
$`V_2(x)`$ $`=`$ $`{\displaystyle \frac{1}{4}}\text{cosec}^2x{\displaystyle \frac{1}{2}}\text{cosec}x\mathrm{cot}x`$ (4. 30)
$$\varphi _0^{(1)}(x)=\sqrt{\mathrm{tanh}\frac{x}{2}},\varphi _0^{(2)}(x)=\sqrt{\mathrm{tan}\frac{x}{2}},e_0^{(1)}=e_0^{(2)}=0$$

From (4.5) and (4.6) it follows that we can reproduce the ground states for the two ES classes.

$$\mathrm{𝟐}.𝐀=\mathbf{\hspace{0.17em}0},𝐁=\mathrm{𝟑}/\mathrm{𝟐}:$$

$`V_1(x)`$ $`=`$ $`{\displaystyle \frac{9}{4}}\text{cosech}^2x{\displaystyle \frac{3}{2}}\text{cosech}x\mathrm{coth}x`$ (4. 31)
$`V_2(x)`$ $`=`$ $`{\displaystyle \frac{9}{4}}\text{cosec}^2x{\displaystyle \frac{3}{2}}\text{cosec}x\mathrm{cot}x`$ (4. 32)
$$\varphi _0^{(1)}(x)=\mathrm{tanh}^{\frac{3}{2}}\frac{x}{2},\varphi _0^{(2)}(x)=\mathrm{tan}^{\frac{3}{2}}\frac{x}{2},e_0^{(1)}=e_0^{(2)}=0$$

Again ground levels for two ES potentials (4.9),(4.10) are reproduced.

$$\mathrm{𝟑}.𝐀=\mathbf{\hspace{0.17em}1}/\mathrm{𝟐},𝐁=\mathrm{𝟏}:$$

$`V_1(x)`$ $`=`$ $`{\displaystyle \frac{7}{4}}\text{cosech}^2x2\text{cosech}x\mathrm{coth}x`$ (4. 33)
$`V_2(x)`$ $`=`$ $`{\displaystyle \frac{7}{4}}\text{cosec}^2x2\text{cosec}x\mathrm{cot}x`$ (4. 34)
$$\varphi _0^{(1)}(x)=\frac{\sqrt{\text{sech}x\mathrm{tanh}x}}{1+\text{sech}x},\varphi _0^{(2)}(x)=\frac{\sqrt{\mathrm{sin}x}}{1+\mathrm{cos}x},e_0^{(1)}=\frac{1}{4}=e_0^{(2)}$$

These are the ground states for the ES classes.

$$\mathrm{𝟒}.𝐀=\mathrm{𝟏}/\mathrm{𝟐},𝐁=\mathrm{𝟐}:$$

$`V_1(x)`$ $`=`$ $`{\displaystyle \frac{19}{4}}\text{cosech}^2x4\text{cosech}x\mathrm{coth}x`$ (4. 35)
$`V_2(x)`$ $`=`$ $`{\displaystyle \frac{19}{4}}\text{cosec}^2x4\text{cosec}x\mathrm{cot}x`$ (4. 36)
$$\varphi _0^{(1)}(x)=\frac{\mathrm{sinh}^{3/2}x}{(1+\mathrm{cosh}x)^2},\varphi _0^{(2)}(x)=\frac{\mathrm{sin}^{3/2}x}{(1+\mathrm{cos}x)^2},e_0^{(1)}=\frac{1}{4}=e_0^{(2)}$$

These are the ground levels for ES potentials.

$$\mathrm{𝟓}.𝐀=\mathbf{\hspace{0.17em}1},𝐁=\mathrm{𝟑}/\mathrm{𝟐}:$$

$`V_1(x)`$ $`=`$ $`{\displaystyle \frac{17}{4}}\text{cosech}^2x{\displaystyle \frac{9}{2}}\text{cosech}x\mathrm{coth}x`$ (4. 37)
$`V_2(x)`$ $`=`$ $`{\displaystyle \frac{17}{4}}cosec^2x{\displaystyle \frac{9}{2}}\text{cosec}x\mathrm{cot}x`$ (4. 38)
$$\varphi _0^{(1)}(x)=\frac{\sqrt{\mathrm{sinh}x}}{(1+\mathrm{cosh}x)^{3/2}},\varphi _1^{(2)}(x)=\frac{\sqrt{\mathrm{sin}x}}{(1+\mathrm{cos}x)^{3/2}},e_0^{(1)}=1=e_1^{(2)}$$

$$\varphi _1^{(1)}(x)=\frac{\sqrt{\mathrm{sinh}x}(\mathrm{cosh}x3)}{(1+\mathrm{cosh}x)^{3/2}},\varphi _0^{(2)}(x)=\frac{\sqrt{\mathrm{sin}x}(\mathrm{cos}x3)}{(1+\mathrm{cos}x)^{3/2}},e_1^{(1)}=0=e_0^{(2)}$$

Here two ES levels are reproduced.

### 4.2 ES class associated to Type II model

Using as before the relations (4.1) and (4.2), we see that in the limit $`k1`$ Type II potential (2.16) goes over to the following ES class known as the generalized Pöschl-Teller potential:

$$V_3(x)=B(B+1)\text{cosech}^2xA(A+1)\text{sech}^2x,$$
(4. 39)
its eigenstates and spectra being given by

$$\psi _r^{(3)}(x)=(\mathrm{cosh}2x1)^{B/2}(\mathrm{cosh}2x+1)^{A/2}P_r^{(B\frac{1}{2},A\frac{1}{2})}(\mathrm{cosh}2x),$$

$$E_r^{(3)}=(A+B2r)^2,(r=0,1,2,\mathrm{}),$$
(4. 40)
where the superscripts indicate correspondance with $`V_3(x)`$.

We recall that the QES levels for Type II model is obtained for half-integer values of $`A`$. Let us now take the ES-limit of the examples given in Subsec. 3.2 \[see equations (3.6)–(3.7)\]. The other parameter $`B`$ is taken as negative real number.

$$\mathrm{𝟏}.𝐀=\frac{\mathrm{𝟏}}{\mathrm{𝟐}}:V_3(x)=B(B+1)\text{cosech}^2x\frac{3}{4}\text{sech}^2x$$
(4. 41)
$$\psi _0^{(3)}(x)=\text{cosech}^Bx\sqrt{\text{sech}x},e_0^{(3)}=\frac{(2B+1)^2}{4}.$$

Here $`\psi _0^{(3)},e_0^{(3)}`$ are ground level for the ES potential $`V_3(x)`$.

$$\mathrm{𝟐}.𝐀=\frac{\mathrm{𝟑}}{\mathrm{𝟐}}:V_3(x)=B(B+1)\text{cosech}^2x\frac{15}{4}\text{sech}^2x$$
(4. 42)
$$\psi _0^{(3)}(x)=\mathrm{sinh}^Bx\mathrm{cosh}^{3/2}x,e_0^{(3)}=(B+\frac{3}{2})^2,$$

$$\psi _1^{(3)}(x)=\frac{\mathrm{sinh}^Bx}{\mathrm{cosh}^{3/2}x}[(2B+1)\mathrm{cosh}^2x2]e_1^{(3)}=(B\frac{1}{2})^2$$

Here $`\psi _{0,1}^{(3)},e_{0,1}^{(3)}`$ are two levels for the ES potential (4.20).

### 4.3 ES class associated to Type III model

The Type III potential (2.17) is defined on the entire real line. This is a QES periodic potential having a real period $`2K`$ and an imaginary period $`4K^{^{}}`$. The algebraic sector is determined for an integer or a half-integer $`A`$, while $`B`$ is arbitrary real parameter. In the limit $`k1`$, this potential coincides to the following ES class:

$$V_4(x)=[B^2A(A+1)]\text{sech}^2x+2B(A+\frac{1}{2})\text{sech}x\mathrm{tanh}x.$$
(4. 43)
The eigenstates and spectra of the potential (4.21) are

$$\psi _r^{(4)}(x)=\text{sech}^Ax\mathrm{exp}[B\mathrm{tan}^1(\mathrm{sinh}x)]P_r^{(iBA\frac{1}{2},iBA\frac{1}{2})}(i\mathrm{sinh}x),$$

$$E_r^{(4)}=(Ar)^2,(r=0,1,2,\mathrm{})$$
(4. 44)
We now take the ES-limit (here $`k1`$ only) of the examples given in Subsec 3.3. Note that the limit $`k0`$ gives a free particle motion.

$$\mathrm{𝟏}.𝐀=\mathrm{𝟎}:V_4(x)=B^2\text{sech}^2x+B\text{sech}x\mathrm{tanh}x$$
(4. 45)
$$\varphi _0^{(4)}(x)=\mathrm{exp}(B\mathrm{tan}^1\mathrm{sinh}x),e_0^{(4)}=0$$

Clearly, the ground state for (4.23) agrees with the general results(4.22) for $`A=0`$.

$$\mathrm{𝟐}.𝐀=\frac{\mathrm{𝟏}}{\mathrm{𝟐}}:V_4(x)=(B^2\frac{3}{4})\text{sech}^2x+2B\text{sech}x\mathrm{tanh}x$$
(4. 46)
$$\varphi _0^{(4)}(x)=\sqrt{\text{sech}x}\mathrm{exp}[B\mathrm{tan}^1(\mathrm{sinh}x)],e_0^{(4)}=1/4$$

This is also in agreement with (4.22) for $`A=1/2`$.

$$\mathrm{𝟑}.𝐀=\mathrm{𝟏}:V_4(x)=(B^22)\text{sech}^2x+3B\text{sech}x\mathrm{tanh}x$$
(4. 47)
$`\varphi _0^{(4)}(x)=\text{sech}x\mathrm{exp}(B\mathrm{tan}^1\mathrm{sinh}x)=\varphi _1^{(4)}(x)`$ , $`e_0^{(4)}=1=e_1^{(4)}`$
$$\varphi _2^{(4)}(x)=\text{sech}x(\mathrm{sinh}x+2B)\mathrm{exp}(B\mathrm{tan}^1\mathrm{sinh}x),e_2^{(4)}=0$$

Thus two ES levels are reproduced from the corresponding QES levels.

Hence we have shown that corresponding to three QES models Type I,Type II and Type III, there is associated some definite ES classes namely $`V_1,V_2`$ (for TypeI),$`V_3`$(for Type II) and $`V_4`$(for Type III) respectively. In the ES limit we can reproduce some ES levels from the corresponding QES levels as well.

## 5 Conclusion

To conclude, we have constructed three new QES elliptic potentials Type I–III using sl(2,$``$) Lie-algebraic scheme and obtained their algebraic levels analytically. Further we have shown that the eigenstates of QES Hamiltonians generate an orthogonal family of polynomials in the energy variable. The interesting point is that the elliptic parameter k($`0<k^2<1`$) in the models turns out to be responsible for QES class and when it touches the end-points 0 and 1 of its domain the ES clsses are revealed. We have explicitly shown that some ES levels can be reproduced on a restricted domain of potential parameters.

## Acknowledgement

I would like to thank Professor B Bagchi for guidance.


text:
# Phonons and specific heat of linear dense phases of atoms physisorbed in the grooves of carbon nanotube bundles

## Abstract

The vibrational properties (phonons) of a one-dimensional periodic phase of atoms physisorbed in the external groove of the carbon nanotube bundle are studied. Analytical expressions for the phonon dispersion relations are derived. The derived expressions are applied to Xe, Kr and Ar adsorbates. The specific heat pertaining to dense phases of these adsorbates is calculated.

Published in Phys. Rev. B 66, 235414 (2002)

I. INTRODUCTION

Adsorption of gases in nanotube materials has been investigated extensively in recent years, both from the experimental  and theoretical  standpoints. A very special geometry of the nanotube materials provides a possibility for realization of unique adsorbate phases with reduced effective dimensionality . The behavior of adsorbates depends on whether they are adsorbed within the tubes, in the interstitial channels, or in the grooves. For samples consisting of nanotubes with closed ends, the adsorption in the tube interior is not possible, and for sufficiently large adsorbates, the adsorption potential in the interstitial channel is purely repulsive. Thus, for the case of large atoms adsorbed in the material made of closed-end carbon nanotubes, the only positions available for gas adsorption are the grooves of the bundles of carbon nanotubes.

In this paper we consider a dense, periodic phase of noble gas atoms physisorbed in the groove positions of a nanotube bundle. This phase can be visualized as a one-dimensional chain of atoms arranged in a periodic array within a groove (see Fig. 1). While the single particle properties of quantum adsorbates in grooves have been considered in Ref. , in this article we concentrate on the many-particle excitations (phonons) of the dense, periodic adsorbate phase, that crucially depend on the interactions between adsorbates.

Recently, measurements of the specific heat of atoms adsorbed in nanotube materials have been reported . In this respect, it is important to theoretically consider the specific heat of a dense phase and its signature in the overall specific heat of the sample (nanotube material + adsorbates).

The outline of the article is as follows. In Sec. II, we present a simple lattice dynamics approach to the vibrations of adsorbates in a groove. We show how the phonon frequencies are related to the interadsorbate interaction potential and the interaction of an adsorbate with the surrounding nanotube medium. In Sec. III, we apply the model from Sec. II to adsorption of Xe, Kr and Ar atoms and we calculate the characteristic vibrational frequencies pertaining to these adsorbates. In Sec. IV, we use this information to calculate the specific heat of dense adsorbate phases. Sec. V summarizes the main results.

II. VIBRATIONS OF DENSE PHASES OF ADSORBATES IN THE GROOVES

To study the vibrations of the adsorbates in a groove we introduce a simplifying assumption of rigid substrate i.e. we do not consider phonons of the nanotube material. In this case, the total potential energy $`\mathrm{\Phi }`$ of the adsorbate system is given as

$$\mathrm{\Phi }=\frac{1}{2}\underset{l,l^{}}{\overset{ll^{}}{}}v(𝐫_l𝐫_l^{})+\underset{l}{}V(𝐫_l).$$
(1)
Here, $`v(𝐫_l𝐫_l^{})`$ represents the interaction between the adsorbates at $`𝐫_l`$ and $`𝐫_l^{}`$ positions. The indices $`l`$ and $`l^{}`$ denote the adsorbed atoms, and $`V(𝐫_l)`$ represents the interaction of the $`l`$-th adsorbate with the surrounding nanotube medium (substrate). We assume that in the absence of vibrations, the adsorbates are positioned in an infinitely long one-dimensional lattice (with the lattice parameter $`a`$, see Fig. 1) within a groove. We also neglect all the interactions between the adsorbates which are not in the same groove. This is an excellent approximation, due to a large diameter of carbon nanotubes.

If the interaction with the substrate were vanishingly small, the problem would reduce to three dimensional vibrations of an unsupported chain of atoms. This problem can be easily solved analytically as shown e.g. in Ref. . Even with the external field $`V`$, the problem can be analytically solved, following the lattice dynamics approach.  The eigen-frequencies of the adsorbate system can be found from the matrix equation

$$[𝒟(q)M\omega (q)^2]𝐞(q)=0,$$
(2)
where $`M`$ is the adsorbate mass, $`\omega (q)`$ is the vibrational frequency, $`q`$ is the phonon wave vector parallel to the groove and $`𝐞(q)`$ is the 3D phonon polarization vector. Note that the phonon wave vector $`q`$ is a one-dimensional quantity since the adsorbate lattice exhibits a 1D translational invariance. The polarization vector $`𝐞(q)`$ is a three-dimensional quantity since the displacements of adsorbate atoms in all three spatial directions are allowed. If we take into account only pair interactions $`v`$ between the nearest neighboring adsorbates and neglect the discrete nature of the tubes surrounding a groove by effectively ”smearing” the carbon atoms along the tube surface , the 3 $`\times `$ 3 dynamical matrix, $`𝒟(q)`$ is given as

$$𝒟=\left[\begin{array}{ccc}2\beta [1\mathrm{cos}(qa)]+f_{xx}& f_{xy}& f_{xz}\\ f_{xy}& 2\alpha [1\mathrm{cos}(qa)]+f_{yy}& f_{yz}\\ f_{xz}& f_{yz}& 2\alpha [1\mathrm{cos}(qa)]+f_{zz}\end{array}\right].$$
(3)
The $`x`$-axis is oriented along the chain of adsorbates, $`y`$-axis passes through the centers of the two tubes surrounding a groove, and the $`z`$-axis in perpendicular to both $`x`$ and $`y`$ axes and points outward from the bundle, as denoted in Fig. 1. The external force constants $`f_{\mu ,\nu }`$ are given by

$$f_{\mu ,\nu }=\left(\frac{^2V}{\mu \nu }\right)_0,\mu ,\nu =x,y,z,$$
(4)
where the subscript zero signifies that the derivatives should be taken at the equilibrium position of the adsorbate. As the tubes surrounding a groove are assumed to be smooth, the external potential, $`V(𝐫_l)`$ does not depend on the adsorbate $`x`$-coordinate and there is no external (substrate induced) restoring force associated with the adsorbate displacements in $`x`$-direction. That is why all $`f_{\mu ,\nu }`$ constants with $`\mu =x`$ or $`\nu =x`$ vanish in Eq. (3). Additionally, due to the symmetry of the external potential with respect to the displacements parallel to the line joining the centers of the two tubes surrounding a groove ($`y`$-direction, see Fig. 1), the constant $`f_{yz}`$ also vanishes.

The force constants associated with the adsorbate-adsorbate interactions \[$`\alpha `$ and $`\beta `$ in Eq. (3)\] are given as

$`\alpha `$ $`=`$ $`{\displaystyle \frac{1}{a}}\left({\displaystyle \frac{dv}{dr}}\right)_{r=a}`$ (5)
$`\beta `$ $`=`$ $`\left({\displaystyle \frac{d^2v}{d^2r}}\right)_{r=a},`$ (6)
where $`r`$ is the coordinate of relative distance between the neighboring adsorbates. The phonon dispersion relations, $`\omega (q)`$ for $`\pi /aq\pi /a`$, obtained as the solutions to Eq. (2) with $`f_{xx}=f_{xy}=f_{xz}=f_{yz}=0`$ are given as

$`\omega _L(q)`$ $`=`$ $`2\sqrt{{\displaystyle \frac{\beta }{M}}}\mathrm{sin}\left({\displaystyle \frac{qa}{2}}\right)`$ (7)
$`\omega _{T1}(q)`$ $`=`$ $`\sqrt{{\displaystyle \frac{f_{yy}+2\alpha [1\mathrm{cos}(qa)]}{M}}}`$ (8)
$`\omega _{T2}(q)`$ $`=`$ $`\sqrt{{\displaystyle \frac{f_{zz}+2\alpha [1\mathrm{cos}(qa)]}{M}}}.`$ (9)
where the subscripts $`L,T1,T2`$ denote the longitudinal ($`L`$) and the two transverse phonon branches ($`T1,T2`$). The $`L,T1`$ and $`T2`$ modes are polarized exclusively in $`x,y`$, and $`z`$ directions, respectively. Similar equations have been derived in Ref. . The authors of this reference considered an isotropic oscillator model, $`V(x,y,z)=\overline{f}[(yy_0)^2+(zz_0)^2]/2`$. The two transverse modes are degenerate in this approximation, which however is not always the case, because generally $`f_{yy}f_{zz}`$, as will be shown in the next section.

A brief comment concerning the neglect of corrugation of the holding potential, i.e. discreteness of the nanotube, is in order here. If the adsorbate phase is commensurate with the holding potential provided by the substrate, the longitudinal mode will exhibit a zone center gap which can be related to the magnitude of the corrugation. This effect has been experimentally confirmed for Xe overlayers on Cu(111) surface  and should in principle be observable for all commensurate systems.

III. VIBRATIONS OF Xe, Kr AND Ar ADSORBATES

The ingredients necessary for the calculation of phonon modes are obviously the force constants $`\alpha ,\beta `$ and $`f_{yy},f_{zz}`$. The first two can be calculated from the presumably known interadsorbate interaction potential, while the $`f`$-force constants can be calculated from the asdsorbate-substrate interaction potential.

The adsorbate-substrate interaction can be calculated as a superposition of the adsorbate-nanotube interactions. It is sufficient to consider only the two nanotubes surrounding the groove, since the interaction of adsorbate atom with other nanotubes is vanishingly small due to a large diameter of the carbon nanotubes typically encountered in experiments.  Neglecting the discrete nature of the carbon nanotube, the adsorbate-single wall nanotube interaction can be written as

$$V(\rho )=3\pi \theta ϵ\sigma ^2\left[\frac{21}{32}\left(\frac{\sigma }{R}\right)^{10}\eta ^{11}M_{11}(\eta )\left(\frac{\sigma }{R}\right)^4\eta ^5M_5(\eta )\right],$$
(10)
where $`ϵ`$ and $`\sigma `$ are the energy and range parameter of the effective adsorbate-carbon site interaction which is assumed to be of a Lennard-Jones form. The variable $`\rho `$ denotes the distance of the adsorbate atom from the axis of the tube, $`\theta `$ is the effective coverage of C atoms on the tube surface ($`\theta `$=0.38 1/Å2), $`R`$ is the tube radius and the variable $`\eta `$ is defined as $`\eta =R/\rho `$ when $`\rho >R`$. The function $`M_n(\eta )`$ is defined as

$$M_n(\eta )=_0^\pi \frac{d\varphi }{(1+\eta ^22\eta \mathrm{cos}\varphi )^{n/2}}.$$
(11)
The external potential can be constructed as a sum of the adsorbate interactions with two tubes surrounding a groove. From the thus constructed potential, the relevant external force constants can be obtained using Eq. (4).

To illustrate the shape of the holding external potential, we plot in Fig. 2 the potential for Xe adsorbate along the $`y`$ and $`z`$ directions. In this figure and in all subsequent calculations, we consider single wall carbon nanotubes with the diameter of 13.8 Å , arranged within a bundle in a triangular lattice with the lattice constant of 17 Å. The origin of the coordinate system is chosen in such a way that the centers of the two tubes surrounding a groove are positioned at $`(y=0`$ Å, $`z=0`$ Å) and ($`y=17.0`$ Å, $`z=0`$ Å). The parameters of the Xe-C site potential are obtained from the so-called combination rules, as explained in Ref. . We adopt all the relevant parameters of adsorbate-adsorbate and adsorbate-substrate interactions from Table I of Ref. . Since the two curves displayed in panels (a) and (b) of Fig. 2 pass through the absolute minimum of the external potential ($`y=8.5`$ Å, $`z=6.38`$ Å), the external force constants can be obtained as second derivatives of the potential curves presented in Fig. 2 at their minimum positions. Note that the potential is significantly more anharmonic in the $`z`$ than in the $`y`$ direction which means that the harmonic approximation to the potential is less satisfactory in the $`z`$-direction as can be seen from inspection of thin dashed lines in Fig. 2 which represent the harmonic approximation. It should be mentioned that the minimum value of the potential we obtain is consistent with the one reported in Ref. . However, the binding energy of a single Xe adsorbate in this potential is not consistent with the experimental result  (-282 $`\pm `$ 11 meV) which is lower than the absolute minimum of the potential we obtain here (-225 meV). A possible small difference in the tube separations at the surface of the bundle with respect to the corresponding separation in the bundle interior may be responsible for this discrepancy. In addition, as shown and discussed in Ref. , small changes in the adsorbate-carbon site effective potential may cause relatively large change in the adsorbate binding energy.

The total adsorbate-adsorbate interaction encompasses direct adsorbate-adsorbate interaction and the indirect interaction mediated by the polarizable substrate material and other adsorbates.  This interaction is generally different from the corresponding interaction between the atoms in the gas phase. The most critical adsorbates to be considered in the remainder of this paper are Xe adatoms which have the highest polarizability of all the adsorbates we shall consider. While the substrate mediated forces can be calculated for a planar substrate material, it is more difficult to calculate them and assess their importance for the substrate of present interest, i.e. a bundle of carbon nanotubes. This issue has been discussed in the case of interstitial adsorption in Ref. .

Even though the many body forces should play a role in dynamics of Xe monolayers on crystal surfaces, it is often found that the gas phase Xe-Xe potentials provide very reliable phonon dispersions . This is in part due to the fact that phonon dispersions are not determined by the potential itself, but by its derivatives which may be less influenced by many-body effects. The only exception to this ”rule” seems to be the somewhat puzzling dynamics of Xe overlayers on Cu surfaces.  In all the calculations to be presented, we shall assume that the adsorbate-adsorbate interactions can be well represented by the corresponding gas phase potentials.

We shall model the adsorbate-adsorbate interaction also by the Lennard-Jones potential, $`4ϵ_{gg}[(\sigma _{gg}/r)^{12}(\sigma _{gg}/r)^6]`$, where $`r`$ is the interadsorbate separation, and $`ϵ_{gg}`$ and $`\sigma _{gg}`$ are the energy and range parameters of the potential, respectively. The equilibrium positions of the adsorbates can be found from the static equilibrium condition, i.e. by minimizing expression (1) with respect to the lattice parameter $`a`$. Following this procedure, we find that the 1D lattice parameter is given by

$$a=\sigma _{gg}\pi \left(\frac{1382}{675675}\right)^{1/6}1.1193\sigma _{gg}.$$
(12)
The force constants $`\alpha `$ and $`\beta `$ \[Eq. (6)\] are then given as

$`\alpha `$ $`=`$ $`0.1665{\displaystyle \frac{ϵ_{gg}}{\sigma _{gg}^2}}`$ (13)
$`\beta `$ $`=`$ $`60.615{\displaystyle \frac{ϵ_{gg}}{\sigma _{gg}^2}}.`$ (14)
Force constant $`\alpha `$ determines the dispersion of the transverse modes. It is negative due to the fact that the lattice parameter $`a`$ is smaller than the equilibrium separation of the binary Lennard-Jones potential (1.122 $`\sigma _{gg}`$). Note also that $`|\alpha ||\beta |`$, which means that the transverse modes have negligible dispersion in comparison with the longitudinal mode.

If the adsorbates form a chain that is commensurate with the substrate corrugation, the periodicity of the one-dimensional chain of atoms may be different from the one obtained here by neglecting the substrate corrugation. In this case, all the force constants may change. On the other hand, for the incommensurate chain, our model should provide reliable results.

In Table I, we summarize the lattice parameters and the force constants needed for calculation of the phonons in the specific cases of Xe, Kr and Ar atoms adsorbed in a groove. We also summarize the mode frequencies at the Brillouin zone center ($`q=0`$) and the zone edge ($`q=\pi /a`$). As can be seen from the table, the transverse modes for all adsorbates considered have completely negligible dispersion throughout the Brillouin zone. We also find that $`\omega _{T1}(q)<\omega _{T2}(q)`$ which is a consequence of a specific shape of the potential experienced by adsorbates in the groove. This means that the potential is ”softer” with respect to adsorbate displacements in the $`z`$-direction (see Fig. 2).

IV. SPECIFIC HEAT OF DENSE ONE-DIMENSIONAL ADSORBATE PHASES

Knowing the dispersion relations for the adsorbate phonons, we can now proceed to calculate the specific heat pertaining to a dense phase of the adsorbates in a groove. The heat capacity at constant volume, $`C_V`$, for a collection of independent oscillators (phonons) is given by

$$C_V=k_B\underset{i}{}\frac{\left(\frac{\mathrm{}\omega _i}{k_BT}\right)^2e^{\mathrm{}\omega _i/k_BT}}{(e^{\mathrm{}\omega _i/k_BT}1)^2},$$
(15)
where $`k_B`$ is the Boltzmann constant, $`T`$ is the temperature, and index $`i`$ counts the harmonic oscillators of frequencies $`\omega _i`$. In our case, the index $`i`$ is replaced by the phonon wave vector, $`q`$ and the phonon branch index $`s`$ ($`s=L,T1,T2`$). Relation (15) is thus rewritten as

$$C_V=\frac{Nk_Ba}{\pi }\underset{s}{}_0^{\pi /a}\frac{\left[\frac{\mathrm{}\omega _s(q)}{k_BT}\right]^2e^{\mathrm{}\omega _s(q)/k_BT}}{[e^{\mathrm{}\omega _s(q)/k_BT}1]^2}𝑑q,$$
(16)
where we have transformed the sum over wave vectors into an integral as $`_q(L_x/2\pi )_{\pi /a}^{\pi /a}𝑑q`$. Here, $`L_x`$ is the length of the adsorbate chain (or groove) and the number of adsorbates within a particular groove is $`N=L_x/a`$. It is easy to check that in the limit of high temperatures ($`k_BT\mathrm{}\omega _s(q),s=L,T1,T2`$), the specific heat in Eq. (16) reduces to its classical value, $`C_V=3Nk_B`$.

In Fig. 3 we plot the specific heat for Xe,Kr and Ar adsorbates obtained from Eq. (16) by using information on the adsorbate phonons summarized in Eq. (9) and Table I. As can be seen, at high temperatures all the three curves tend to the classical limit.

To separate the influence of transverse modes, we plot in Fig. 4 the three different contributions to the specific heat of a chain of Xe atoms, i.e. in the sum in Eq. (16) we consider only one mode (either $`L,T1`$, or $`T2`$). As can be inferred from this figure, the low temperature behavior of the specific heat ($`T<4`$ K) is completely determined by the longitudinal mode. At temperatures higher than about 4 K (for Xe), all the modes in the sum in Eq. (16) must be considered. Due to the fact that the transverse modes have higher frequencies for Kr and Ar adsorbates, their contribution to the specific heat becomes significant at somewhat higher temperatures. The specific heat at low temperatures, where only the L mode contributes, is proportional to the temperature and the following relation holds:

$$C_V2.095Nk_B\frac{k_BT}{\mathrm{}\omega _L(q=\pi /a)}.$$
(17)
The linear dependence of specific heat on temperature is a consequence of effectively 1D behavior of the chain at low temperatures and can be easily seen from Fig. 3 at temperatures lower than $``$ 4K. Equation (17) also implies that the measurement of specific heat at low temperatures would yield an information on the maximum frequency of the longitudinal mode (Brillouin zone edge frequency). As this frequency crucially depends on the interadsorbate potential \[Eq. (6) and Eq. (9)\], these measurements could yield an information on the effective interaction between the adsorbate atoms which may be modified by the presence of the substrate material, as discussed in Sec. III.

V. SUMMARY

We have studied the vibrational properties of linear dense phases of adsorbates in the grooves of the carbon nanotube bundles. The three modes characterizing the adsorbate vibrations have been identified and their frequencies have been calculated for Xe, Kr and Ar adsorbates. We have also calculated the specific heat corresponding to the linear phase and identified the temperature regimes in which the transverse modes begin to significantly contribute to the specific heat. The presented results should serve as a useful guidance in the measurements of specific heat of gases adsorbed in the nanotube materials.

ACKNOWLEDGMENTS

I thank dr. Branko Gumhalter and Marko T. Cvitaš for a careful reading of the manuscript. I thank prof. Milton W. Cole for bringing Ref.  to my attention.