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# Towards an understanding of CMR pyrochlore Tl2Mn2O7

## I INTRODUCTION

Since its discovery in 1996, the colossal magnetoresistance (CMR) exhibited by the pyrochlore compound Tl2Mn2O7 posed many interesting questions. First among them, whether a common fundamental mechanism could be responsible for the origin of CMR both in this compound and in the larger family of perovskite manganese oxides, which have different crystal structure and electronic properties. The recent appearance of CMR in other compounds with the pyrochlore crystal structure  exhibiting long range ferromagnetic ordering, and the larger experimental background now existent, allow a better standpoint to approach the theoretical description of this compound.

Tl2Mn2O7 undergoes a ferromagnetic transition with critical temperature $`T_c`$ 125K (also reported as 140K), below which temperature the compound exhibits long range ferromagnetic ordering and is metallic. A sharp decrease in resistivity with the development of spontaneous magnetization below $`T_c`$, and the magnetoresistance maximum around $`T_c`$ with field induced magnetization, which are similar to those of CMR Mn-perovskites, indicate that a strong coupling between transport and magnetism also exists in Tl2Mn2O7. But important differences have been established with respect to the CMR perovskites, starting from its A2B2O7 “pyrochlore” crystal structure. No Mn3+ has been detected, so that the associated Jahn-Teller structural distortions as well as a possible double exchange (DE) mechanism inducing ferromagnetism between Mn3+-Mn4+ pairs, studied in connection with CMR in perovskite manganites, are absent. The crystal structure is almost temperature independent around $`T_c`$, no structural anomalies appear which could be associated with the change in magnetotransport properties, thus evidencing negligible spin-lattice correlations. Structural analysis indicate negligible O deficiencies present in stoichiometric Tl2Mn2O7, and recently specially synthesized Tl2-xMn2O7-y defect compounds show the development of spin-glass behavior subjacent to ferromagnetism. Magnetization measurements for the stoichiometric compound have shown saturation values of e.g. $`\mu _S`$ 2.59, 2.7, 2.8, 3 $`\mu _B`$, which are in general slightly lower than the 3$`\mu _B`$ expected for Mn4+ ions with a $`3d^3`$ ($`S=3/2`$) configuration. Hall experiments have indicated a very small number of high mobility electron-like carriers: $``$0.001-0.005 conduction electrons per formula unit, differing notably with the hole-doped Mn-perovskites where CMR appears around 30$`\%`$ doping. The critical temperature $`T_c`$ has been reported to show a negative pressure dependence, again in contrast to CMR perovskites, though above 10 Kbar a change of tendency and positive pressure shifts of $`T_c`$ in Tl2Mn2O7 have been reported. Recently, also striking differences with the perovskites were reported for the evolution of the charge dynamics probed in optical conductivity measurements. Experimental research of magnetotransport has also been actively pursued in other pyrochlore compounds where the ordered phase remains insulating, as well as in many obtained by substitutional doping of the diverse components of Tl2Mn2O7.

The experimental results have received various interpretations and prompted different proposals and suggestions for the mechanism potentially involved in CMR in Tl2Mn2O7 since 1996. Already in Refs. 3 and 13 it was suggested that magnetism and transport seemed related primarily to two different subsystems, unlike DE invoked for CMR perovskites: magnetism (suggested to be possibly driven by superexchange) involving mostly Mn-$`3d`$ and O orbitals, while transport would be mainly determined by carriers involving highly itinerant Tl-$`6s`$ orbitals mixed with oxygen. Unusually large scattering from spin fluctuations accompanying the FM ordering in the presence of low carrier densities was suggested as explanation for CMR. Electronic structure calculations for Tl2Mn2O7 indicated that the bands immediately below the Fermi level correspond mainly to Mn-$`t_{2g}`$ states, above the Fermi level appear Tl-$`6s`$ bands, while O states are mixed with these around the Fermi level. The band structure calculation by Singh  obtained a strong spin differentiation in the electronic structure around the Fermi level in the ferromagnetic ground state. The majority spin Mn-$`t_{2g}`$O-$`2p`$ bands below the Fermi level are separated by a gap from the Mn-$`e_g`$ derived bands, though there is also a mixing with Tl and O states above and below the Fermi level. Thus a small near band edge Fermi surface is obtained. For the minority channel instead, a highly dispersive band with a strong admixture of Mn, Tl and O was found around the Fermi level, leading to a metallic minority spin channel. In Ref. 3 it was also mentioned that the Hall data could result from a small number of carriers in the Tl-$`6s`$ band: assuming Tl$`{}_{}{}^{3+}{}_{2x}{}^{}`$Tl$`{}_{}{}^{2+}{}_{x}{}^{}`$Mn$`{}_{}{}^{4+}{}_{2x}{}^{}`$Mn$`{}_{}{}^{5+}{}_{x}{}^{}`$O7 with x$``$ 0.005 the data could be accounted for, indicating a very small doping into the Mn4+ state. In 1997, this proposal was explored in terms of an intermediate valence model (IVM) for Tl2Mn2O7 by Alascio and one of us (C.I.V.). Hall experiments  and CMR results  could be accounted for in the context of the strongly differentiated electronic structure obtained, with temperature and magnetic field changes which allowed explanations for the drastic carrier density changes which had been observed at $`T_c`$ in Hall data, proposing the presence of a (spin-dependent) hybridization gap or pseudogap near the Fermi level. It may be mentioned that while Mn5+ is a rarely found oxidation state for Mn, in Tl2Mn2O7 it could effectively appear as a result of the strong hybridization of orbitals near the Fermi level. Furthermore, recently the presence of Mn5+ ions has been reported in Cd-substituted samples (Tl2-xCdxMn2O7) together with Mn4+ ions, while in a different context Mn5+ in a tetrahedral environment has been found to exist in Ba3Mn2O8.

In 1998, Majumdar and Littlewood  explored the scenario of spin fluctuations around $`T_c`$ in presence of very low carrier densities proposed in Refs. 3 and 13, starting from the proposal of a microscopic model involving Hund and superexchange coupling, and showing that spin polarons might form and provide an explanation for CMR. An electronic structure calculation by Mishra and Sathpathy in 1998 shows some common features with the IVM band structure: in the FM phase they mention the presence of a free-electron-like minority spin $`\mathrm{\Gamma }_1`$ band crossing the Fermi energy with highly mobile carriers. They relate this band to Mn-$`t_{2g}`$ and Tl-$`6s`$ orbitals hybridized with O, the Mn-$`e_g`$ orbitals being higher in energy. The occupied majority-spin bands consist of a Mn$`t_{2g}`$/O band, and a small pocket of very heavy holes, unimportant for transport. They propose a ferromagnetic double exchange Hamiltonian for Tl2Mn2O7 with a very small number of $`\mathrm{\Gamma }_1`$ Zener carriers which align anti-parallel to the localized Mn$`t_{2g}`$ spins, including a weak AF-superexchange interaction between the localized spins. Recent optical conductivity measurements  are consistent with the main features of the electronic structure calculations mentioned. Recently, an explanation of the origin and pressure dependence of ferromagnetism has been put forward in terms of a conventional FM superexchange model, provided that the intra-atomic Hund interactions in oxygen are also taken into account and the empty Mn$`e_g`$ orbitals hybridize with the O and Tl levels.

In this paper we aim to contribute to the understanding of CMR in Tl2Mn2O7 by presenting our investigation of the magnetic phase diagram and electronic structure of a generic model for the compound, which is based on the suggestions presented by many researchers proposing the presence of superexchange interactions (of either sign) between nearest neighbor Mn4+ ions, and the indications of previous band structure calculations. In Section II we introduce this generic model for Tl2Mn2O7, and make a brief presentation of the mean-field treatment that we have employed in our study. Section III exhibits the results which we obtained for different sets of parameters, including those that have been suggested by various authors  as possibly relevant for the description of this compound. A comparison is also made with the electronic structure obtained before using the IVM model, discussing the similar features which it has been possible to exhibit between them. In Section IV a summary of our study of the HS model, and comments on the present status of the understanding of the pyrochlore compound Tl2Mn2O7 are presented.

## II  A MODEL FOR Tl2Mn2O7 INCLUDING HUND AND SUPEREXCHANGE COUPLINGS

In this section we introduce a generic model for Tl2Mn2O7 based on the suggestions presented by many researchers, general enough to allow us to make a comparative study between the various proposals which it includes as particular cases. The generic model takes into account the now widely accepted fact that in this material transport and magnetism seem to be primarily related to different electronic orbitals,  which we describe by two bands of different character which are hybridized. One band is mainly itinerant, and the other includes strong correlations, as we now describe. The correlated electrons appear forming a lattice of local magnetic moments, and also occupying a narrow band, which are coupled via a strong Hund exchange interaction. This would correspond to the assumption that the local magnetic moments present in the material are due to Mn4+ ions, with occupied Mn-$`t_{2g}`$ orbitals which, however, due to their mixing with O orbitals below the Fermi level, are not completely localized, giving rise to the narrow band. A hybridization exists between the correlated band and the mostly itinerant one, which is connected with the low lying conduction states involving Tl$`6s`$ orbitals and O levels (eventually hybridized with the mostly empty Mn-$`e_g`$ orbitals) in accordance with most experimental suggestions mentioned above, band structure calculations, and the recent description of the pressure dependence of $`T_c`$ for various CMR pyrochlores. The possibility of a superexchange coupling between the localized spins being present is also considered.

Concretely, the generic model that we have studied is described by the Hamiltonian

$$H=H_c+H_d+H_V+H_S,$$
(1)
where:

$`H_c`$ $`=`$ $`t_c{\displaystyle \underset{i,j\sigma }{}}(c_{i\sigma }^{}c_{j\sigma }+\text{H.c.})\mu {\displaystyle \underset{i\sigma }{}}c_{i\sigma }^{}c_{i\sigma },`$ (2)
$`H_d`$ $`=`$ $`t_d{\displaystyle \underset{i,j\sigma }{}}(d_{i\sigma }^{}d_{j\sigma }+\text{H.c.})+(\epsilon _d\mu ){\displaystyle \underset{i\sigma }{}}d_{i\sigma }^{}d_{i\sigma },`$ (3)
$`H_V`$ $`=`$ $`V{\displaystyle \underset{i\sigma }{}}\left(c_{i\sigma }^{}d_{i\sigma }+d_{i\sigma }^{}c_{i\sigma }\right),`$ (4)
$`H_S`$ $`=`$ $`J_\mathrm{H}{\displaystyle \underset{i}{}}𝐒_i𝐬_i^{(d)}J_S{\displaystyle \underset{i,j}{}}𝐒_i𝐒_j.`$ (5)
In this Hamiltonian $`H_c`$ describes the band associated to the weakly (here simplified as un-) correlated carriers in Tl2Mn2O7, characterized by a hopping parameter $`t_c`$ between nearest neighbors, and a creation operator $`c_{i\sigma }^{}`$ for an electron with spin $`\sigma `$ in the respective Wannier orbital centered on site $`i`$. $`H_d`$ describes the narrow band associated to the correlated orbitals, characterized by a hopping parameter $`t_d`$, and a creation operator $`d_{i\sigma }^{}`$ for an electron with spin $`\sigma `$ in the Wannier orbital of reference energy $`\epsilon _d`$ (with respect to the center of the $`c`$ band) localized on site $`i`$. The chemical potential of the system is denoted by $`\mu `$, and is determined by the total electronic filling $`n`$. The following term of the Hamiltonian describes a hybridization, $`H_V`$, between the $`c`$ and $`d`$ electron bands, which we assume to be local, for simplicity.

The last term of the Hamiltonian, $`H_S`$, describes the Hund (or Kondo-like) coupling $`J_H`$ between the localized spins $`𝐒_i`$ (which would represent the spin operator associated to a Mn4+ ion at site $`i`$, for example) and the itinerant spins, denoted by $`𝐬_i^{(d)}`$, corresponding to the narrow $`d`$ band associated to the correlated electron orbitals related to Mn in Tl2Mn2O7. A Heisenberg exchange term is also included in the spin Hamiltonian $`H_S`$ to allow for a superexchange interaction $`J_S`$ effective between the local moments of nearest neighbor Mn ions. The sign convention was chosen such that any positive spin coupling constant describes a ferromagnetic (FM) interaction, while negative ones will denote antiferromagnetic (AF) coupling.

To study the magnetic phase diagram and electronic structure of the system described by the general Hamiltonian introduced above \[hereafter to be denoted also as the Hund-superexchange (HS) model\], we have employed the mean field approximation as briefly discussed below.

### A Ferromagnetic phase

We investigated the existence of a uniform ferromagnetic phase, introducing two order parameters to characterize it:

$`M`$ $`=`$ $`S_i^z,`$ (6)
$`m`$ $`=`$ $`s_i^{(d)z}{\displaystyle \frac{1}{2}}d_i^{}d_id_i^{}d_i,`$ (7)
denoting by $`<O>`$ the thermal (quantum) average of operator $`O`$ in the system at temperature $`T`$ ($`T=0`$, for the system in its ground state).

The corresponding mean-field Hamiltonian, after Fourier transforming the band terms, takes the form

$`H_F^{\mathrm{MF}}`$ $`=`$ $`{\displaystyle \underset{𝐤\sigma }{}}\left[\stackrel{~}{ϵ}_c(𝐤)n_{𝐤\sigma }^c+\stackrel{~}{ϵ}_{d\sigma }(𝐤)n_{𝐤\sigma }^d\right]+V{\displaystyle \underset{𝐤\sigma }{}}\left(c_{𝐤\sigma }^{}d_{𝐤\sigma }+d_{𝐤\sigma }^{}c_{𝐤\sigma }\right)`$ (9)
$`{\displaystyle \underset{i}{}}\left(J_Hm+zJ_SM\right)S_i^z+J_HMmN+{\displaystyle \frac{1}{2}}NzJ_SM^2,`$
where the Hund and Heisenberg exchange couplings have been decoupled as usual in mean field approximation. $`N`$ stands for the total number of lattice sites, $`z`$ is the coordination number, and we have defined

$`\stackrel{~}{ϵ}_c(𝐤)`$ $``$ $`ϵ_𝐤^c\mu ,`$ (10)
$`\stackrel{~}{ϵ}_{d\sigma }(𝐤)`$ $``$ $`ϵ_𝐤^d\mu \sigma J_HM/2,`$ (11)
in terms of the dispersion relations for the bare $`c`$ and $`d`$ bands, $`ϵ_𝐤^c=t_c_𝜹e^{i𝐤𝜹}`$ and $`ϵ_𝐤^d=\epsilon _dt_d_𝜹e^{i𝐤𝜹}`$, where $`𝜹`$ describes the vectors connecting any one lattice site with its $`z`$ nearest neighbors, and $`n_{k,\sigma }^\alpha \alpha _{k,\sigma }^{}\alpha _{k,\sigma }`$ , with $`\alpha =c,d;\sigma =,`$.

The first two terms on the RHS of Eq. (9) describe two hybridizing bands, one of them subject to an effective magnetic field \[through the product $`J_HM`$ appearing in $`\stackrel{~}{ϵ}_{d\sigma }(𝐤)`$, Eq. (11)\]. The third term corresponds to an array of independent localized spins in the effective field arising from their original mutual interaction as well as their interaction with the $`d`$-band electrons. Finally, the last terms are additive constants produced by the mean-field decoupling.

The band part of the mean-field Hamiltonian $`H_F^{\mathrm{MF}}`$ is easily diagonalized, yielding the energy eigenvalues

$$E_\pm ^\sigma (𝐤)=\frac{1}{2}\left[\stackrel{~}{ϵ}_c(𝐤)+\stackrel{~}{ϵ}_{d\sigma }(𝐤)\pm \sqrt{[\stackrel{~}{ϵ}_c(𝐤)\stackrel{~}{ϵ}_{d\sigma }(𝐤)]^2+4V^2}\right],$$
(12)
which represent the ferromagnetic bands for spin $`\sigma `$. The corresponding eigenvectors allow us to write the electron operators of the $`c`$ and $`d`$ bands as combinations of operators related to the new hybrid bands (and vice-versa), which is used in the calculation of the relevant averages.

At a given temperature $`T`$, and for a fixed total band filling $`n`$, the magnetization order parameters can be calculated self-consistently through their definitions, Eqs. (6) and (7), while the chemical potential can be determined by the self-consistency condition for the total number of electrons occupying the ferromagnetic bands. We chose to rewrite this in terms of the original $`c`$ and $`d`$ band fillings (denoted $`<n_c>`$ and $`<n_d>`$, respectively):

$$n=<n_c>+<n_d>.$$
(13)
Finally, the free energy per site of the ferromagnetic solution,

$$F=F_B+F_S+F_0,$$
(14)
is evaluated as the sum of three terms: the band free energy, the localized spins contribution, and additive energy constants. These terms are respectively given by

$`F_B`$ $`=`$ $`T{\displaystyle \underset{𝐤\sigma }{}}{\displaystyle \underset{\alpha =\pm }{}}\mathrm{ln}\left[1+e^{E_\alpha ^\sigma (𝐤)/T}\right],`$ (15)
$`F_S`$ $`=`$ $`T\mathrm{ln}\mathrm{Tr}\left[e^{(J_Hm+zJ_SM)S^z/T}\right],`$ (16)
$`F_0`$ $`=`$ $`J_HMm+{\displaystyle \frac{1}{2}}zJ_SM^2+\mu n.`$ (17)
The last term in Eq. (17) must be added to compensate for the inclusion of the chemical potential in the Hamiltonian defined previously. Notice that we are dropping the Boltzmann constant, which implies that temperature will be expressed in the same units as energy.

### B Antiferromagnetic phase

We also investigated the existence of an antiferromagnetic phase. Such long-range magnetic ordering would appear frustrated in the real pyrochlore lattice, but as a first approach, we study here a simplified version of the problem on a cubic lattice. In this case, the lattice is divided into two interpenetrating equivalent sublattices with opposite magnetizations, labeled $`A`$ and $`B`$ respectively. By symmetry, only two order parameters which describe the sublattice magnetizations characterize this phase:

$`S_i^z`$ $`=`$ $`\{\begin{array}{cc}\hfill M,& iA,\hfill \\ \hfill M,& iB,\hfill \end{array}`$ (20)
$`s_i^{(d)z}`$ $`=`$ $`\{\begin{array}{cc}\hfill m,& iA,\hfill \\ \hfill m,& iB,\hfill \end{array}`$ (23)
where both $`M`$ and $`m`$ are positive-defined quantities.

The procedure used to determine the antiferromagnetic solution in mean field approximation is similar to the one presented above for the ferromagnetic phase. For completeness, we will only include here the form assumed by the mean-field Hamiltonian, $`H_{\mathrm{AF}}^{\mathrm{MF}}`$, written in terms of operators characterizing the two interpenetrating sublattices:

$`H_{\mathrm{AF}}^{\mathrm{MF}}`$ $`=`$ $`\mu {\displaystyle \underset{𝐤\sigma }{}}\left(a_{𝐤\sigma }^{}a_{𝐤\sigma }+b_{𝐤\sigma }^{}b_{𝐤\sigma }\right)+{\displaystyle \underset{𝐤\sigma }{}}ϵ_𝐤^c\left(e^{i𝐤𝜹_0}a_{𝐤\sigma }^{}b_{𝐤\sigma }+\text{H.c.}\right)`$ (27)
$`+{\displaystyle \underset{𝐤\sigma }{}}\left[\left(\epsilon _d\mu \sigma J_HM/2\right)A_{𝐤\sigma }^{}A_{𝐤\sigma }+\left(\epsilon _d\mu +\sigma J_HM/2\right)B_{𝐤\sigma }^{}B_{𝐤\sigma }\right]`$
$`+{\displaystyle \underset{𝐤\sigma }{}}(ϵ_𝐤^d\epsilon _d)\left(e^{i𝐤𝜹_0}A_{𝐤\sigma }^{}B_{𝐤\sigma }+\text{H.c.}\right)+V{\displaystyle \underset{𝐤\sigma }{}}\left(a_{𝐤\sigma }^{}A_{𝐤\sigma }+b_{𝐤\sigma }^{}B_{𝐤\sigma }+\text{H.c.}\right)`$
$`{\displaystyle \underset{i=1}{\overset{N/2}{}}}\left(J_HmzJ_SM\right)\left[S_i^{z(A)}S_i^{z(B)}\right]+J_HMmN+{\displaystyle \frac{1}{2}}zJ_SM^2N.`$
Here we have introduced two-site unit cells to describe the AF lattice and used the following notation: $`d_{i\sigma }=A_{i\sigma }(B_{i\sigma })`$ for $`iA(B)`$; $`c_{i\sigma }=a_{i\sigma }(b_{i\sigma })`$ for $`iA(B)`$; explicit indication of sublattice is made for localized-spin operators; $`𝜹_0`$ is a vector connecting the two sites (one belonging to each sublattice) inside a unit cell. Notice that the wave-vector sums are now performed over the reduced Brillouin zone of the AF lattice.

The determination of the self-consistent AF solution follows along the same lines as in the FM case, except that we have to obtain numerically the eigenvalues and eigenvectors of the itinerant part of the effective Hamiltonian (27), as we are now dealing with a 4x4 matrix.

## III RESULTS AND DISCUSSION

In this section we present some of the results we have obtained for the generic HS model introduced in the previous section using many different sets of parameters: including those which have been suggested by various authors  as possibly relevant for the description of Tl2Mn2O7. We want to stress that even with the simplifications adopted in the present treatment, notwithstanding the known over-estimation of critical temperatures and other limitations to be mentioned, which are inherent to the mean-field approximation used, it is nevertheless interesting to be able to exhibit features in common with the different models that have been proposed for Tl2Mn2O7 if appropriate relevant sets of parameters are chosen. This will be the aim of the presentation of results and discussion in this section.

For simplicity and without much loss of generality, we assume the localized spins to have $`S=1/2`$. In this case, the mean-field self-consistency equations for the magnetization order parameter $`M`$ \[Eqs. (6) and (20), respectively\], assume the simple form

$$M=\frac{1}{2}\mathrm{tanh}\left[\frac{1}{2T}\left(J_Hm\pm zJ_SM\right)\right],$$
(28)
where the upper (lower) sign corresponds to the ferromagnetic (antiferromagnetic) solution.

We have assumed a three-dimensional simple cubic lattice ($`z=6`$), and used a semi-elliptic approximation for the bare densities of states (DOS). The $`c`$ band half-bandwidth $`W=zt_c`$ is used as the energy unit. To fix ideas in the following discussion we will choose that value to be $`1e`$V, in qualitative agreement with experiments and band-structure calculations. We also consider anti-homotetic bands, i.e., $`t_d=\alpha t_c`$, $`\alpha `$ being a (positive) narrowing factor. This would be consistent with an electron-like $`c`$ band related to the mobile carriers, and a narrower hole-like $`d`$ band.

We have investigated the existence of magnetically ordered solutions for many sets of parameters of the HS model. Both FM and AF solutions are obtained at low temperatures for wide ranges of parameter values. This puts into evidence a strong competition between these two kinds of ordering in the model. We select the physically relevant solution in each case by comparing the free energies and choosing the lowest one. In this paper we present ground-state phase diagram results (at temperatures much lower than the critical ones for either magnetic phase, $`T<<T_{c_{(F)}},T_{c_{(AF)}}`$, where full spin polarization has been established) for which the bare $`d`$ band has been centered at an energy $`\epsilon _d=0.7e`$V (the bare $`c`$ band being centered at the origin). This is consistent with the $`d`$ band lying near the bottom of the $`c`$ band, which will yield a small number of conduction electrons. Our phase diagrams are plotted as functions of the bandwidth ratio $`\alpha `$ and the superexchange-coupling strength $`J_S`$. In each phase diagram the following remaining parameters have been fixed: the Hund-coupling strength $`J_H`$ (kept at a large value, comparable to the width of the conduction band), the hybridization $`V`$ and the total electron filling $`n`$.

A fact worth noticing is a symmetry manifest in the mean-field Hamiltonians (Eqs. (9) and (27), respectively): the system is invariant under a simultaneous change of sign of the Hund-coupling $`J_H`$ and of the relative orientation between magnetizations $`m`$ and $`M`$. Thus, the system will not distinguish energetically between a situation corresponding to a FM-like Hund-coupling, in which case the magnetizations $`M`$ and $`m`$ will be parallel, and the case of AF-like Hund coupling, in which these two magnetizations would have relative anti-parallel orientations. Taking this symmetry into account, one can restrict the analysis to positive $`J_H`$, as expected on physical grounds for this compound.

We present phase-diagrams obtained for a range of electron fillings around $`n=1`$, near the region of interest for the description of Tl2Mn2O7 as will be discussed shortly in connection with the electronic structure and occupation of the bands.

First, we will discuss the phase-diagrams obtained including an antiferromagnetic superexchange (SE) coupling between nearest neighbor spins, as some authors have suggested: $`J_S0`$. We can make a few general statements:

i) for small enough hybridization (e.g. $`V=0.02e`$V ) no ferromagnetism is obtained for any finite value of AF-superexchange in the large region of variation of the bandwidth ratio $`\alpha `$ investigated ($`0\alpha 0.5`$ ) for fillings around $`n=1`$;

ii) at larger hybridization values (e.g., $`V=0.2,0.3,0.4e`$V ) an interesting competition between AF and F is obtained as a function of the parameters, including reentrant behavior as a function of $`\alpha `$. Though antiferromagnetism widely dominates for $`n=1`$, we also found that for weak AF-superexchange, $`0.01eVzJ_S0`$, pockets of ferromagnetism appear at small to intermediate values of $`\alpha `$. In Fig. 1(a) we show how these FM pockets shift to larger $`\alpha `$ values if the hybridization is increased.

Larger electron fillings \[see Fig. 1(b)\] increase the size of the ferromagnetic regions, which are now obtained also at smaller $`\alpha `$ values (narrower bare $`d`$ band). To exemplify the dependence of the phase diagram with electron filling at fixed hybridization we include Fig. 2 corresponding to hybridization $`V=0.3e`$V, where the cases $`n=1,1.09,1.15`$ are shown. The effect of filling on the phase diagram is amplified for larger hybridization values.

Thus, varying the filling, in the presence of a hybridization large enough, and for a $`d`$ band relatively narrower than the $`c`$ band, we have demonstrated that ferromagnetism can be obtained from the HS model even in the presence of a (weak) AF-superexchange($`J_S0`$), as has been suggested before, the stability region growing with increasing hybridization.

If the phase diagram in the presence of a weak FM superexchange interaction ($`J_S>0`$) is now investigated, as proposed early on for this compound by many researchers, and later claimed to be effectively the case if a careful consideration of the effect of O-orbitals was undertaken, of course the ferromagnetic phase is favored. Now much larger ranges of the bandwidth ratio $`\alpha `$ correspond to ferromagnetic ground states, as can be appreciated in Figs. 1 and 2.

The subtle interplay of the different parameters which has been shown to determine the magnetic ordering in the HS model, in particular needed to obtain a ferromagnetic ground state for example, can be quite easily understood if one analyzes the corresponding electronic band structure. As seen in Fig. 3, where we plot the density of states decomposed in terms of the original bands, we find that for the parameter ranges in which ferromagnetism is clearly stable for the HS model, strong spin differentiation exists in the electronic structure. A band gap connected to the majority-spin orbitals is present at the Fermi level ($`E_F`$), while a finite density of states at $`E_F`$ is obtained mainly for the minority-spin conduction band $`c_{}`$. For the fillings which have been discussed above, the chemical potential of the system is located near a hybridization band gap edge (see Fig. 3), providing occupation of the different orbitals in qualitative agreement with previous electronic structure calculations. These results are also interesting as they place us in an analogous scenario to that proposed in 1997 for this compound, when the IVM for Tl2Mn2O7 was introduced and shown to provide an explanation for the results obtained in Hall experiments and the colossal nature of the MR of the compound. The presence of the Fermi level near band edges, e.g. of a hybridization gap or pseudogap, in a strongly spin differentiated electronic band structure, and especially the spin-dependent conduction band changes predicted as a function of temperature and magnetic field, were shown to originate drastic changes in the carrier concentration around $`T_c`$ which, in the absence of anomalous Hall contributions, could be directly related to the measurements in Hall experiments  and explain them. The validity of the Hall data analysis performed in Ref. 23 has recently been confirmed by new experimental reports on Hall and thermopower data over wider temperature and magnetic field ranges. In Ref. 14 the new Hall data are successfully explained using the same approach of Ref. 23, and support the prediction of drastic carrier density changes near $`T_c`$, related to conduction band changes due to the development of magnetization, as being the main sources for the observed magnetotransport properties.

Due to the simple mean-field approximation adopted, only at low temperatures, when the system is fully polarized, are our phase diagram results trustful, and the electronic structure results suitable for comparison with those obtained before using the IVM. The effect of spin-polarization by the Hund interaction is not correctly estimated here at higher temperatures, being included only through the mean field magnetization order parameters. In fact, an investigation of the critical temperatures obtained here also evidenced problems related to the inability of the MFA employed to treat adequately the strong Hund correlations: the Curie temperatures obtained are found to decrease as hybridization is increased (which one would tend to connect with negative pressure coefficients for $`T_c`$ as experimentally observed ) even in cases for which the phase diagrams show a stabilization of ferromagnetic ordering with increase of the hybridization (as we obtain for fillings $`n>1`$). This seems caused by a spurious tendency to stabilize a local magnetization due to the mutual interaction between the localized spins and the $`d`$ electrons through their Hund coupling, irrespective of the intersite interactions, due to the mean field approximation employed. Thus, the shortcomings of the present treatment for all but the lowest temperatures prevent us from addressing here the interesting issue of the ability of the HS model to describe the effect of pressure on $`T_c`$ for different values of its parameters. The increase of spin disorder with temperature, and in particular the paramagnetic phase, should be much better described using the coherent potential approximation as in Ref. 23 for the IVM. We expect that such a treatment for the paramagnetic phase of the Hund-superexchange model would allow us to exhibit similarities with the IVM electronic structure results above $`T_c`$, like those shown to exist for the ferromagnetic phase in the present work, and to address other issues of interest outside the scope of the simple treatment presented in this work.

## IV SUMMARY

Increasing experimental evidence on magnetotransport in Tl2Mn2O7 points towards drastic changes in the carrier concentration around $`T_c`$ as being mainly responsible for its colossal magnetoresistance. The absence of anomalous contributions to the Hall resistance has also recently been confirmed. Since the nature of the carriers involved in magnetotransport has been established as free electron-like, there are now strong indications in favor of a direct relationship between drastic changes in the conduction band structure around $`T_c`$ and the observed magnetotransport properties.

A strongly spin-differentiated electronic band structure, with drastic changes in the conduction bands around the critical temperature, seems a natural way to explain such abrupt carrier concentration changes. The presence of hybridization gaps or pseudogaps which, depending on the spin orientation of the carriers, might change drastically at $`T_c`$ would allow for such a scenario.

The present paper is a first approach to show how such a scenario, first proposed for Tl2Mn2O7 in 1997 in connection with an intermediate valence model (IVM) introduced to describe CMR and Hall data of the compound, can effectively also be realized starting from different microscopic models suggested for Tl2Mn2O7, involving Hund and superexchange magnetic couplings, as well as hybridization effects. We have performed a detailed study of the stability of magnetically ordered phases obtained at low temperatures for various sets of parameters of a generic Hund-superexchange model (HS). The model is based on the assumption that the Mn orbitals, besides providing localized magnetic moments, also show some degree of delocalization through hybridization with the other orbitals, thus yielding a narrow band strongly coupled to the localized moments via a Hund coupling. This narrow band also shows strong hybridization with a broader conduction band, related to the carriers in the compound. The possibility of a superexchange interaction between the localized spins is also allowed for in the generic model, thereby including many of the proposals presented before for this compound. The electronic structure of the HS model was also investigated, obtaining for the ferromagnetic case a strong spin differentiation and the presence of a minority-spin metallic channel, thus exhibiting many similarities with the electronic structure derived from the IVM for this ordered phase. The simple mean-field approach adopted here is unsuitable to describe adequately the effects of the Hund interaction as temperature is increased. This limits the validity of our results to temperatures well below the critical one. It also prevents us from discussing the ability of the Hund-superexchange model to describe the pressure dependence of $`T_c`$ in its various parameter regimes.

Nowadays the mechanism responsible for the long-range ferromagnetism experimentally observed in Tl2Mn2O7 has not yet been conclusively identified. The results presented here, those obtained before with the IVM, as well as the conclusions of much recent experimental work mentioned here, seem to indicate that in fact, provided the transport remains metallic, the detailed model for the magnetism matters much less than the trend with carrier density, as has been pointed out before for Tl2Mn2O7. In fact, our magnetic phase diagram results show that, although a ferromagnetic superexchange interaction between the Mn localized moments might be necessary to explain ferromagnetism in the related insulating pyrochlores (for example, where Y or Lu appear substituting Tl), the enhanced stability of FM ordering in Tl2Mn2O7 can be connected to the presence of spin-polarized charge carriers and hybridization effects, in accordance with previous suggestions. Careful analysis of spectroscopic experiments is needed to elucidate conclusively whether the drastic changes observed in carrier concentration are mainly related to magnetization-related changes of the conduction bands themselves and/or shifts of the conduction band edges.

###### Acknowledgements.

We especially thank Blas Alascio for enlightening discussions, and acknowledge financial support from the Argentina-Brazil cooperation program SECYT-CAPES BR/A99-EIII18/00. M.A.G. was also supported by grant PRONEX/FINEP/CNPq 41.96.0907.00 (Brazil).


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# “Dynamical” non-minimal higher-spin interaction and gyromagnetic ratio 𝑔=2

## Acknowledgements

This work has been done in the frame of the project no. 0380178S98 financed by the Ministry of Education of Estonia and partially supported by the Estonian Science Foundation, grants nos. 3458 and 4510.


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# Quantum Chaos at Finite Temperature

## 1 Introduction

Deterministic chaos has been observed in a huge number of phenomena in macroscopic i.e. classical physics. But chaotic phenomena were also found in microscopic physics ruled by quantum mechanics – an area presently under very active investigation. For reviews see Refs.. For example, the hydrogen atom in a strong magnetic field shows strong irregularities in its spectrum . Irregular patterns have been found in the wave functions of the quantum mechanical stadium billard . Billard like boundary conditions have been realized experimentally in mesoscopic quantum systems, like quantum dots and quantum corrals, formed by atoms in semi-conductors .

Classical chaos theory can not simply be taken over to quantum physics (due to Heisenberg’s uncertainty relation). Hence workers have tried to characterize quantum chaos in ways alternative to classical chaos. A fruitful approach is Gutzwiller’s periodic orbit theory  which predicts level densities in the semi-classical regime (Rydberg states in atoms). Wintgen  applied it to the diamagnetic hydrogen system and was able to extract periodic orbit information from experimental level densities. Another successful route is the analysis of level densities in the context of random matrix theory. A conjecture by Bohigas et al.  states that the signature of a classical chaotic system is described by random matrix theory and its spectral density follows a Wigner distribution.

Strictly speaking, there is no universally accepted definition of quantum chaos. Many roads have been travelled searching for ”irregular” signals in quantum systems. In the quest for quantum chaos, it has been popular to examine systems which exhibit classical chaos. However, Jona-Lasinio et al.  found chaotic behavior in a quantum system without classical counterpart, i.e., a quantum many-body system undergoing multiple resonant tunneling. Jona-Lasinio and Presilla  further studied quantum many-body systems of interacting bosons in the thermodynamic limit. They found chaotic signals when the interaction strength drives the system away from integrability.

Signals of quantum chaos have been investigated also in fermionic many-body systems, in particular by looking at the Poisson versus Wigner level spacing distributions . Georgeot and Shepelyansky  studied a spinglass model of spin $`1/2`$ particles and looked at the transition from the integrable to the chaotic regime, when tuning a random transverse magnetic field. Casetti et al.  considered the large $`N`$ limit of $`N`$-component $`\varphi ^4`$ oscillators in the presence of an external field. They compare classical chaos with quantum chaos, computed in mean field theory. They observe a strong suppression of quantum chaos due to quantum corrections moving the system away from a hyperbolic fixed point responsable for classical chaos. Habib et al.  have studied in chaotic systems the relation between classical and quantum expectation values. They found divergence between the two after a time scale $`t_{\mathrm{}}ln(C/\mathrm{})`$. Decoherence reduced this discrepancy.

However, the study of quantum chaos lacks from the following shortcomings: (i) In quantum chaos, we have no ”local” information of the degree of chaoticity, being available in classical chaos via Lyapunov exponents and Poincaré sections from phase space. (ii) Also little is known about the role of temperature in quantum chaos. For example, the analysis of level densities is insensitive to temperature. To overcome those problems, we adopt the strategy of building a bridge between quantum physics and classical physics. This means a relation involving the quantum transition amplitude and the classical action. Starting from the path integral, the following ”bridges” have been considered:

(i) Sum over classical paths. The quantum mechanical transition amplitude can be expressed via the path integral. In certain cases this path integral can be expressed as a sum over classical paths only. This holds, e.g. for the harmonic oscillator. Unfortunately, such relation holds only in a few exceptional cases .

(ii) Gutzwiller’s trace formula. Gutzwiller  has established a relation between the density of states of the quantum system and a sum over classical periodic orbits (periodic orbit quantisation). The trace formula has been applied in the semi-classical regime (e.g. highly excited states of atom). Wintgen  applied it to the diamagnetic hydrogen system and extracted periodic orbit information from experimental level densities.

(iii) Effective action. Another possibility is to use the convential effective action . An effective action has been also considered at finite temperature . The effective action has been introduced in such a way that it gives an expectation value $`<\varphi >=\varphi _{class}`$ which corresponds to the classical trajectory and which minimizes the potential energy (effective potential). Thus one can obtain the ground state energy of the quantum system from its effective potential. Because the effective action has a mathematical structure similar to the classical action, it looks like the ideal way to bridge the gap from quantum to classical physics and eventually solve the quantum chaos and quantum instanton problem. Cametti et al. have computed in Q.M. the effective action perturbatively via loop ($`\mathrm{}`$) expansion and studied quantum chaos in the 2-D anharmonic oscillator. Perturbation theory forces to terminate such series at a finite (low) order. The difficulty lies in the estimation of the remainder. This poses a problem in the context of chaos, because chaotic systems are known to exhibit sensitivity not only to initial conditions but also to parameters of the system. There are higher loop corrections to the effective potential $`V^{eff}`$ as well as to the mass renormalisation $`Z`$. The kinetic term of the effective action is given by an asymptotic series of higher time derivatives (infinite series of increasing order). The problem in interpreting $`\mathrm{\Gamma }`$ as effective action is that those higher time derivatives require more intial/boundary conditions than the classical action.

(iv) Bohm’s interpretation of quantum mechanics. An interesting approach has been taken by Iacomelli and Pettini . They have used Bohm’s  interpretation of quantum mechanics, which expresses the Schrödinger equation in polar form. The radial part satisfies a continuity equation of a velocity field and the phase satisfies a Hamilton-Jacobi equation. The ”trajectories” of the quantum system are equivalent to Lagrangian trajectories of the fluid velocity field. This allows to apply the concept of classical chaos theory and in particular compute Lyapunov exponents. In Ref. this framework has been used to study the chaotic behavior of the hydrogen atom in an external magnetic field and different regimes of quantum chaoticity have been observed.

## 2 Quantum Action

In the following we will explore the quantum action  as bridge between classical and quantum physics. This action has a mathematical structure like the classical action, and takes into account quantum effects (quantum fluctuations) via renormalized action parameters. The quantum action has the following attractive properties : (i) It can be computed non-perturbatively, via numerical simulations. (ii) It is defined for arbitrary finite temperature. (iii) In the zero-temperature limit analytic expressions exist for the quantum action, provided that the classical potential is sufficiently symmetric (parity symmetric in D=1 and rotationally symmetric in D=2,3). (iv) In a numerical study of the 1-D anharmonic oscillator, we searched for the presence of higher order time derivative terms in the kinetic term of the quantum action. No signal for such term was found . The quantum action has proven useful for rigorous definition and quantitative computation of quantum instantons . Let us recall the definition of the quantum action, as proposed in Ref.
Conjecture: For a given classical action $`S=𝑑t\frac{m}{2}\dot{x}^2V(x)`$ there is a quantum action $`\stackrel{~}{S}=𝑑t\frac{\stackrel{~}{m}}{2}\dot{x}^2\stackrel{~}{V}(x)`$, which allows to express the transition amplitude by

$$G(x_{fi},t_{fi};x_{in},t_{in})=\stackrel{~}{Z}\mathrm{exp}[\frac{i}{\mathrm{}}\stackrel{~}{S}[\stackrel{~}{x}_{cl}]|_{x_{in},t_{in}}^{x_{fi},t_{fi}}].$$
(1)
Here $`\stackrel{~}{x}_{cl}`$ denotes the classical path, such that the action $`\stackrel{~}{S}(\stackrel{~}{x}_{cl})`$ is minimal (we exclude the occurrence of conjugate points or caustics). $`\stackrel{~}{Z}`$ denotes the normalisation factor corresponding to $`\stackrel{~}{S}`$. Eq.(1) is valid with the same action $`\stackrel{~}{S}`$ for all sets of boundary positions $`x_{fi}`$, $`x_{in}`$ for a given time interval $`T=t_{fi}t_{in}`$. The parameters of the quantum action depend on the time $`T`$. Any dependence on $`x_{fi},x_{in}`$ enters via the trajectory $`\stackrel{~}{x}_{cl}`$. $`\stackrel{~}{Z}`$ depends on the action parameters and $`T`$, but not on $`x_{fi},x_{in}`$.

The quantum action at finite time $`T`$ can be interpreted as action at finite temperature. The partition function in quantum mechanics requires to go over from real time to imaginary time and to impose periodic boundary conditions . In Ref. we have shown that the expectation value of a quantum mechanical observable $`O`$ at thermodymical equilibrium can be expressed in terms of the quantum action along its classical trajectory from $`x_{in}`$, $`\beta _{in}=0`$ to $`x`$, $`\beta `$, given by

$`\stackrel{~}{\mathrm{\Sigma }}_\beta \stackrel{~}{S}_\beta [\stackrel{~}{x}_{cl}]|_{x_{in},0}^{x,\beta }={\displaystyle _0^\beta }𝑑\beta ^{}{\displaystyle \frac{m}{2\mathrm{}^2}}({\displaystyle \frac{d\stackrel{~}{x}_{cl}}{d\beta ^{}}})^2+\stackrel{~}{V}(\stackrel{~}{x}_{cl})`$
$`{\displaystyle \frac{\delta \stackrel{~}{S}_\beta }{\delta x}}[\stackrel{~}{x}_{cl}]=0`$
$`\stackrel{~}{x}_{cl}(\beta _{in})=x_{in},\stackrel{~}{x}_{cl}(\beta )=x,`$ (2)
where $`T`$ denotes the absolute value of imaginary time. The parameters $`\beta `$, temperature $`\tau `$ and $`T`$ are related by $`\beta =\frac{1}{k_B\tau }=T/\mathrm{}`$. In numerical studies with the quartic potential in 1-D we found the parameters of the quantum action to be temperature dependent .

## 3 Analytic form of quantum action at zero temperature

Why are we interested in the zero-temperature limit? First, from the experimental point of view, the ground state properties of a quantum system are often much better known than excited states. Second, zero temperature corresponds to large time and from the point of view of chaos theory, it is interesting to study dynamical behavior at large times. Examples: (a) Behavior of particles moving in storage rings, (b) In classical Hamiltonian chaos, there are quasi-periodic trajectories, remaining for a long time in the vicinity of regular islands. What is the corresponding behavior in quantum mechanics? (c) What is the quantum analogue of the KAM theorem? (d) The construction of Poincaré sections and Lyapunov exponents involves long time trajectories. Likewise the quantum analogue of Poincaré sections and Lyapunov exponents will require long time evolutions.

In the following we work in imaginary time. In order to avoid notational confusion, we continue to use the time parameter $`T`$. In particular, $`T0`$ denotes the high temperature limit, where the quantum action approaches its classical counter part. $`T\mathrm{}`$ denotes the zero-temperature limit, where the quantum action is determined by the Feynman-Kac formula. In Ref. the following analytic transformation law at temperature zero has been derived in 1-D relating the classical action $`S=𝑑t\frac{1}{2}m\dot{x}^2+V(x)`$ to the quantum action $`\stackrel{~}{S}=𝑑t\frac{1}{2}\stackrel{~}{m}\dot{x}^2+\stackrel{~}{V}(x)`$,

$$2m(V(x)E_{gr})=2\stackrel{~}{m}(\stackrel{~}{V}(x)\stackrel{~}{v}_0)\frac{\mathrm{}}{2}\frac{\frac{d}{dx}2\stackrel{~}{m}(\stackrel{~}{V}(x)\stackrel{~}{v}_0)}{\sqrt{2\stackrel{~}{m}(\stackrel{~}{V}(x)\stackrel{~}{v}_0)}}\text{sgn}(x).$$
(3)
Moreover, the following relation between the ground state wave function and the quantum action holds

$$\psi _{gr}(x)=\frac{1}{N}e^{_0^{|x|}𝑑x^{}\sqrt{2\stackrel{~}{m}(\stackrel{~}{V}(x^{})\stackrel{~}{v}_0)}/\mathrm{}},E_{gr}=\stackrel{~}{v}_0,$$
(4)
Eqs.(3,4) are valid under the assumption of a parity symmetric potential $`\stackrel{~}{V}(x)`$ with a unique minimum at $`x=0`$, $`\stackrel{~}{V}(0)=\stackrel{~}{v}_0`$. Similar laws hold for rotationally symmetric potentials in D=2 and 3. For a number of systems, where the ground state energy and wave function is known analytically, it has been shown  that the quantum action reproduces exactly the ground state energy and wave function. Examples in 1-D are: Monomial potentials and the inverse square potential. Examples for radial motion in 3-D are: Monomial potentials and Coulomb potential (hydrogen atom) in the sector of non-zero angular momentum. In particular, the ground state energy coincides with the minimum of the quantum potential $`\stackrel{~}{V}`$ and the location of the minimum of the quantum potential coincides with the location of the maximum of the wave function. One should note that the transformation law, Eq.(3), determines mass $`\times `$ potential, but not both, mass and potential individually. The determination of the renormalized mass requires an non-perturbative numerical calculation.

In the following we will try to estimate the precision of numerical calculations of the quantum action in the zero-temperature limit (long time limit) by contrasting it with the analytic expressions of Eqs.(3,4). We consider in 1-D the classical action

$`S`$ $`=`$ $`{\displaystyle 𝑑t\frac{m}{2}\dot{x}^2}+V(x),V(x)=v_2x^2+v_4x^4,`$
$`m`$ $`=`$ $`1`$
$`v_2`$ $`=`$ $`1`$
$`v_4`$ $`=`$ $`0.01.`$ (5)
The Q.M. Hamiltonian has the following ground state energy,

$$E_{gr}=0.710811.$$
(6)
For the quantum action we make an ansatz

$$\stackrel{~}{S}=𝑑t\frac{\stackrel{~}{m}}{2}\dot{x}^2+\stackrel{~}{V}(x),\stackrel{~}{V}(x)=\stackrel{~}{v}_0+\stackrel{~}{v}_2x^2+\stackrel{~}{v}_4x^4+\stackrel{~}{v}_6x^6.$$
(7)
From a fit of the quantum action to Q.M. transition amplitudes (for more details see Ref.) we find the action parameters at $`T=4.5`$

$`\stackrel{~}{m}=0.9990(7)`$
$`\stackrel{~}{v}_0=0.79863(1)`$
$`\stackrel{~}{v}_2=1.013(2)`$
$`\stackrel{~}{v}_4=0.0099(9)`$
$`\stackrel{~}{v}_6=0.0000(3).`$ (8)
The parameters $`\stackrel{~}{m}`$, $`\stackrel{~}{v}_2`$, $`\stackrel{~}{v}_4`$, $`\stackrel{~}{v}_6`$ have asymptotically stabilized at about $`T=4.5`$. However, the parameter $`\stackrel{~}{v}_0`$ has a slow fall-off behavior for $`T\mathrm{}`$. For large $`T`$ we have fitted $`\stackrel{~}{v}_0`$ to the numerical data by

$$\stackrel{~}{v}_0(T)_T\mathrm{}A+\frac{B}{T}+\frac{C}{T^2},$$
(9)
and find $`A=0.710819`$. Thus the asymptotic extrapolation $`\stackrel{~}{v}_0(T\mathrm{})=0.710819`$ is very close to $`E_{gr}`$, given by Eq.(6). This confirms $`E_{gr}=\stackrel{~}{v}_0`$, predicted by Eq.(4), i.e. the ground state energy is given by the minimum of the quantum potential. Let us further check the consistency of other parameters of the quantum potential. This can be done by using the transformation law Eq.(3). Because this transformation law does not determine $`\stackrel{~}{m}`$, we have taken $`\stackrel{~}{m}`$ from the numerial data. The transformation law then determines the parameters of the quantum potential. We find,

$`\stackrel{~}{v}_2`$ $`=`$ $`{\displaystyle \frac{2}{\stackrel{~}{m}}}[mE_{gr}/\mathrm{}]^2=1.01151`$
$`\stackrel{~}{v}_4`$ $`=`$ $`{\displaystyle \frac{2}{3}}{\displaystyle \frac{\sqrt{2\stackrel{~}{m}\stackrel{~}{v}_2}}{\mathrm{}}}[\stackrel{~}{v}_2v_2{\displaystyle \frac{m}{\stackrel{~}{m}}}]=0.009967`$
$`\stackrel{~}{v}_6`$ $`=`$ $`{\displaystyle \frac{1}{4}}{\displaystyle \frac{\stackrel{~}{v}_4^2}{\stackrel{~}{v}_2}}+{\displaystyle \frac{2}{5}}{\displaystyle \frac{\sqrt{2\stackrel{~}{m}\stackrel{~}{v}_2}}{\mathrm{}}}[\stackrel{~}{v}_4v_4{\displaystyle \frac{m}{\stackrel{~}{m}}}]=2.8910^7.`$ (10)
This is consistent with the numerical results, given by Eq.(3). Finally, let us look at the ground state wave function. As reference solution, we have solved the Schrödinger equation with the original Hamiltonian. Secondly, we computed the wave function from the quantum action via Eq.(4), using the numerical data given by Eq.(3). The comparison is given in Fig., showing good agreement. In summary of this section, we have shown for the zero-temperature limit (regime of the Feynman-Kac formula) that the transition amplitude can be parametrized by the quantum action. A comparison of analytical versus numerical computation of the quantum action has shown good agreement.

## 4 Quantum chaos in 2-D anharmonic oscillator

As is well known 1-D conservative systems with a time-independent Hamiltonian are integrable and do not display classical chaos. An interesting candidate system to display chaos is the K-system, corresponding to the potential $`V=x^2y^2`$. It decribes a 2-D Hamiltonian system, being almost globally chaotic, having small islands of stability . However, according to a suggestion by Pullen and Edmonds , it is more convenient from the numerical point of view to consider the following system, which also exhibits classical chaos. It is a 2-D anharmonic oscillator, defined by the following classical action,

$`S`$ $`=`$ $`{\displaystyle _0^T}𝑑t{\displaystyle \frac{1}{2}}m(\dot{x}^2+\dot{y}^2)+V(x,y),V(x,y)=v_2(x^2+y^2)+v_{22}x^2y^2`$
$`m`$ $`=`$ $`1`$
$`v_2`$ $`=`$ $`0.5`$
$`v_{22}`$ $`=`$ $`0.05.`$ (11)
We work in imaginary time and the convention $`\mathrm{}=k_B=1`$ is used. For the corresponding quantum action, we make the following ansatz, compatible with time-reversal symmetry, parity conservation and symmetry under exchange $`xy`$,

$`\stackrel{~}{S}`$ $`=`$ $`{\displaystyle _0^T}𝑑t{\displaystyle \frac{1}{2}}\stackrel{~}{m}(\dot{x}^2+\dot{y}^2)+\stackrel{~}{V}(x,y),`$
$`\stackrel{~}{V}`$ $`=`$ $`\stackrel{~}{v}_0+\stackrel{~}{v}_2(x^2+y^2)+\stackrel{~}{v}_{22}x^2y^2+\stackrel{~}{v}_4(x^4+y^4).`$ (12)
We have determined numerically the parameters of the quantum action for transition times from $`T=0`$ up to $`T=4`$, where a regime of asymptotic stability is reached. For $`T=4`$ corresponding to temperature $`\tau =0.25`$, we found

$`\stackrel{~}{m}`$ $`=`$ $`0.99814(6)`$
$`\stackrel{~}{v}_0`$ $`=`$ $`1.29373(2)`$
$`\stackrel{~}{v}_2`$ $`=`$ $`0.5154(3)`$
$`\stackrel{~}{v}_{22}`$ $`=`$ $`0.0497(1)`$
$`\stackrel{~}{v}_4`$ $`=`$ $`.0008(7).`$ (13)
We have included terms $`\dot{x}\dot{y}`$, $`xy`$, $`xy^3+x^3y`$. Their coefficients were found to be very small (compared to machine precision). Also we included terms $`x^2y^4+x^4y^2`$, $`x^4y^4`$. Those coefficients were found compatible with zero within error bars. The quantum action slightly modifies the parameters $`\stackrel{~}{v}_2`$ and the parameter $`\stackrel{~}{v}_{22}`$.

Like it was done in sect. for the 1-D case, we would like to check also in the 2-D system how well the quantum action reproduces the ground state properties in the zero-temperature limit. The classical action considered now is neither rotationally symmetric, nor integrable. Nevertheless, we can express the ground state energy and wave function in terms of the quantum action, and compare it with the solution of the Schrödinger equation. We use the property of $`\stackrel{~}{V}(\stackrel{}{x})`$ having a unique minimum at $`\stackrel{}{x}=0`$. In the limit $`T\mathrm{}`$ using conservation of energy, $`\stackrel{~}{T}_{kin}+\stackrel{~}{V}=ϵ=\stackrel{~}{v}_0`$, the quantum action can be evaluated along its classical trajectory, with boundary conditions $`\stackrel{~}{\stackrel{}{x}}_{cl}(t=0)=\stackrel{}{x}_{in}`$ and $`\stackrel{~}{\stackrel{}{x}}_{cl}(t=T)=\stackrel{}{x}_{fi}`$ to yield

$`\stackrel{~}{\mathrm{\Sigma }}\stackrel{~}{S}[\stackrel{~}{\stackrel{}{x}}_{cl}]|_{\stackrel{}{x}_{in},0}^{\stackrel{}{x}_{fi},T}={\displaystyle _0^T}𝑑t\stackrel{~}{T}_{kin}+\stackrel{~}{V}={\displaystyle _0^T}𝑑t2\stackrel{~}{T}_{kin}+ϵ`$
$`_T\mathrm{}\stackrel{~}{v}_0T+\stackrel{~}{m}{\displaystyle _0^T}𝑑t({\displaystyle \frac{d\stackrel{~}{\stackrel{}{x}}_{cl}}{dt}})^2=\stackrel{~}{v}_0T+\stackrel{~}{m}\left({\displaystyle _0^{T/2}}+{\displaystyle _{T/2}^T}𝑑t({\displaystyle \frac{d\stackrel{~}{\stackrel{}{x}}_{cl}}{dt}})^2\right)`$
$`=\stackrel{~}{v}_0T+\stackrel{~}{m}\left({\displaystyle _{\stackrel{}{x}_{in}}^0}+{\displaystyle _0^{\stackrel{}{x}_{fi}}}𝑑\stackrel{~}{\stackrel{}{x}}_{cl}({\displaystyle \frac{d\stackrel{~}{\stackrel{}{x}}_{cl}}{dt}})\right).`$ (14)
Using the conjecture, Eq.(1), gives the transition amplitude

$$G(\stackrel{}{x}_{fi},T;\stackrel{}{x}_{in},0)_T\mathrm{}\stackrel{~}{Z}_0e^{\stackrel{~}{v}_0T/\mathrm{}}\mathrm{exp}[\stackrel{~}{m}_0^{\stackrel{}{x}_{fi}}𝑑\stackrel{~}{\stackrel{}{x}}_{cl}\frac{d\stackrel{~}{\stackrel{}{x}}_{cl}}{dt}]\mathrm{exp}[\stackrel{~}{m}_{\stackrel{}{x}_{in}}^0𝑑\stackrel{~}{\stackrel{}{x}}\frac{d\stackrel{~}{\stackrel{}{x}}_{cl}}{dt}],$$
(15)
where we subsumed $`\stackrel{~}{Z}/\stackrel{~}{Z}_0`$ into $`\stackrel{~}{\mathrm{\Sigma }}`$ and $`\stackrel{~}{Z}_0`$ is a constant of dimension $`1/L^D`$. Comparison with the Feynman-Kac formula yields the ground state energy and wave function,

$$E_{gr}=\stackrel{~}{v}_0,\psi _{gr}(\stackrel{}{x})=\frac{1}{N}\mathrm{exp}[\stackrel{~}{m}_0^\stackrel{}{x}𝑑\stackrel{~}{\stackrel{}{x}}_{cl}\frac{d\stackrel{~}{\stackrel{}{x}}_{cl}}{dt}],$$
(16)
where $`\stackrel{~}{\stackrel{}{x}}_{cl}`$ is the trajectory from $`\stackrel{~}{\stackrel{}{x}}_{cl}(t=T/2)=o`$ to $`\stackrel{~}{\stackrel{}{x}}_{cl}(t=T)=\stackrel{}{x}`$. The ground state wave function thus obtained from the quantum action has been compared to the solution of the Schrödinger equation. This is shown in Fig.. We also compared the ground state energy. The solution of the stationary Schrödinger equation yields $`E_{gr}=1.01207`$. Like in the 1-D system (see Eq.(4)) the ground state energy is given by the minimum of the quantum potential. Extrapolation of $`\stackrel{~}{v}_0`$ to large $`T`$ yields $`\stackrel{~}{v}_01.0127`$. One observes that the quantum action describes well the physics at zero temperature also of the 2-D anharmonic oscillator. Compared to the 1-D system, however, the error in the wave function is larger by one order of magnitude. A reason is certainly due to the fact that in 1-D we have an analytical expression (4) for the wave function from the quantum action, while in 2-D this is not available.

Now let us look at the chaotic behavior of the classical and the quantum action. We have computed Poincaré sections from the classical action and from the quantum action for a variety of temperatures. The equations of motion of the quantum action have been solved using a 4-th order Runge-Kutta algorithm, and Henon’s algoritm was used to compute the Poincaré sections. Let us discuss what we expect. First, the classical system under consideration is chaotic due to the anharmonic interaction term. This term is small compared to the harmonic oscillator term. This property proliferates to the quantum potential. Here ”smallness” is meant in the following sense: The quantum system at zero temperature is determined by the ground state properties. We have computed $`r_0=r_{gr}`$, the radius of the ground state wave function (corresponding to the Bohr radius $`a_0`$ in the hydrogen atom). We obtain $`r_0=0.8766`$. It turns out that the anharmonic term is smaller than the harmonic term for any length $`r<r_0`$. Thus one expects roughly the same ”amount” of chaotic behavior in the quantum system as in the classical system. Second, renormalisation (i.e. change of action parameters when going from the classical action to the quantum action) tends to increase harmonic terms, i.e. drive the system to a Gaussian fixed point. At a Gaussian fixed point the system is integrable. i.e. non-chaotic. This effect has been observed in a number of numerical studies in 1-D systems . In a system with a symmetric double well potential this effect was found to lead to a softening of the double well shape of the quantum potential (lower barrier, more narrow minima, even vanishing of the double well). This translates to a softening or even an ”evaporation” of quantum instantons compared to the classical instantons . This effect is present also in the system under consideration here. We find $`\delta \stackrel{~}{v}_2=\stackrel{~}{v}_2v_2=0.0154(3)`$ compared to $`\delta \stackrel{~}{v}_{22}=\stackrel{~}{v}_{22}v_{22}=.0003(1)`$. We expect that this effect may lead to a slight softening of the chaotic behavior in the quantum system. Third, a weak anharmonic term means that the quantum potential reaches a regime of asymptiotic stability as function of $`T`$ already for small $`T`$ ($`T4`$). That is, when going from high to low temperature, already at relatively high temperature the asymptotic regime (Feynman-Kac limit) is reached.

We computed the Poincaré sections for the quantum action at temperature $`\tau =0.25`$ (corresponding to $`T=4`$) for energies $`E=10,20,50`$. One should keep in mind that the classical action at $`T=0`$ is equivalent to a quantum action at temperature $`\tau =\mathrm{}`$. Those Poincaré sections compared to their counter part from the classical action are shown in Figs.\[3-5\]. One observes that the quantum system also displays chaos, and the Poincaré sections are slightly different from those of the classical action. Like in the classical case also in the quantum system the ”amount” of chaoticity increases with increasing energy. Moreover, the difference between classical and quantum Poincaré sections becomes more accentuated with increase of energy. For comparison, we also display in Fig. the Poincaré sections of the quantum action at $`E=50`$ for temperature $`\tau =2`$ and $`\tau =0.5`$, i.e. closer to the high temperature limit.

## 5 Summary

We have discussed the use of the quantum action, which can be considered as a renormalized classical action at finite temperature. Based on the quantum action we suggest a proper definition of quantum chaos and explore it numerically. As example, we have considered in 2-D the harmonic oscillator with a weak anharmonic coupling and computed the quantum action at various temperatures. We compared Poincaré sections of the quantum action with those of the classical action and found some difference in their chaotic behavior.

Acknowledgements
H.K. and K.M. are grateful for support by NSERC Canada. X.Q.L. has been supported by NSF for Distinguished Young Scientists of China, by Guangdong Provincial NSF and by the Ministry of Education of China.

Figure Caption

1-D anharmonic oscillator. Ground state wave function from Schrödinger equation (open dots) and from quantum action (squares). Their difference is shown in the lower part.

Ground state wave function of 2-D anharmonic oscillator. $`x`$ indicates the location of cuts through the wave function. The upper part shows the solution from Schrödinger equation (full line) and from quantum action (different symbols). The difference is shown in the lower part.

2-D anharmonic oscillator. Poincaré sections at energy $`E=10`$. Upper part classical action, lower part quantum action at temperature $`\tau =0.25`$.

Same as Fig., but $`E=20`$.

Same as Fig., but $`E=50`$.

Poincaré sections of quantum action at $`E=50`$, $`\tau =2`$ and $`\tau =0.5`$.


text:
# Quantum-dot lithium in zero magnetic field: Electronic properties, thermodynamics, and a liquid-solid transition in the ground state

## I Introduction

Quantum dots  are artificial electron systems (ES) realizable in modern semiconductor structures. In these systems two-dimensional (2D) electrons move in the plane $`z=0`$ in a lateral confinement potential $`V(x,y)`$. The typical length scale $`l_0`$ of the lateral confinement is usually larger than or comparable with the effective Bohr radius $`a_B`$ of the host semiconductor. The relative strength of the electron-electron and electron-confinement interaction, given by the ratio $`\lambda l_0/a_B`$, can be varied, even experimentally, in a wide range, so that the dots are used to be treated as artificial atoms with tunable physical properties. Experimentally, quantum dots were intensively studied in recent years, using a variety of different techniques, including capacitance , transport , far-infrared  and Raman spectroscopy .

From the theoretical point of view, quantum dots are ideal physical objects for studying effects of electron-electron correlations. Different theoretical approaches, including analytical calculations , exact diagonalization , quantum Monte Carlo (QMC) , density functional theory  and other methods , were applied to study their properties, for a recent review see Ref. . Until recently most theoretical work was performed in the regime of strong magnetic fields, when all electron spins are fully polarized. In the past three years a growing interest is observed in studying the quantum dot properties in zero magnetic field $`B=0`$ . The aim of these studies is to investigate the Fermi liquid – Wigner solid crossover in the dots, at a varying strength of Coulomb interaction. Detailed knowledge of the physics of such a crossover in microscopic dots could be compared with that obtained for macroscopic 2DES  and might shed light on the nature of the metal-insulator transition in two dimensions .

So far, full energy spectra of an $`N`$-electron parabolic quantum dot in zero magnetic field, as a function of the interaction parameter $`\lambda `$, were published only for $`N=2`$ (quantum-dot helium ). For larger $`N`$ a number of results for the ground state energy of the dots were reported at separate points of the $`\lambda `$ axis. Sometimes, however, results obtained by different methods contradict to each other, and full understanding of physical properties of $`N`$-electron dots at $`B=0`$ has not yet been achieved.

Even for three electrons in a parabolic confining potential (quantum-dot lithium) available in the literature results are somewhat confusing and do not give a clear and exact picture of the ground state of the dot. Egger et al. reported in  on a transition from a partly to a fully spin-polarized ground state at $`\lambda 5`$ caused by the intra-dot Coulomb interaction ($`z`$-component of the total spin $`S_z^{tot}`$ changes from $`1/2`$ to $`3/2`$). This conclusion was based on results of QMC calculations (multilevel blocking algorithm). For the $`1/2`$ state calculations gave at $`\lambda =4`$ slightly lower energy, than for the $`3/2`$ state, and higher energies at $`\lambda =6`$, 8 and 10. In a subsequent (Erratum) publication  other (corrected) values for the energy of these states were reported. At $`\lambda =4`$ they gave the same energies of the 1/2 and 3/2 states. The conclusion from these two publications in the part concerning the three-electron quantum dot is thus not clear. Häusler , calculating the energy spectrum of a three-electron dot using the so-called pocket state method, gave a more definite indication on the existence of such a transition. He presented his results, however, in some specific for the method and not-directly related to $`\lambda `$ units, which does not allow one to quantitatively characterize the transition (e.g. to get the value of the interaction parameter $`\lambda `$ at the transition point). Häusler also pointed out that some indications on such a transition can be also seen in earlier studies of a three-electron dot: in Ref.  ($`\lambda 2`$) the ground state of the dot at $`B=0`$ was found to be partly spin-polarized, while in Ref.  with a substantially larger value of $`\lambda `$ the fully spin-polarized state turned out to have the lower energy. As seen from this brief outline, available data indicate that this transition seems to exist but it is not yet quantitatively understood, and its physical origin is not completely clear. It is also not clear whether and how this transition in the spin state of the system is related to the Fermi-liquid – Wigner-molecule transition in the dot.

In this paper I present results of a complete theoretical study of a three-electron parabolic quantum dot. Using exact diagonalization technique, I calculate full energy spectrum of the dot, as a function of the interaction parameter in the range $`0\lambda 10`$. At $`\lambda =\lambda _c=4.343`$ I find a transition in the ground state of the dot, accompanied by the change of the total spin quantum number. I study the densities and the pair-correlation functions in the ground and the first excited states of the system at a number of $`\lambda `$-points, including the vicinity of the transition. These results show that physical properties of the dot dramatically change at the transition point, corresponding to properties of Fermi liquid at $`\lambda <\lambda _c`$, and of a Wigner molecule at $`\lambda >\lambda _c`$. I also calculate some thermodynamic properties of the dot: the heat capacity and the volume-pressure diagram. The temperature dependence of the heat capacity clearly exhibits characteristic features, related to the transition, in the temperature range corresponding to a few K for typical parameters of GaAs dots. Other experimental consequences from predictions of this paper are also discussed.

In Section II I briefly describe the model and the method used in calculations. Results of the work are presented in Section III. Concluding remarks can be found in Section IV.

## II Model and method

### A The Hamiltonian

I consider three 2D electrons moving in the plane $`z=0`$ in a parabolic confining potential $`V(r)=m^{}\omega _0^2r^2/2`$, $`𝐫=(x,y)`$. The Hamiltonian of the system

$$\widehat{H}=\underset{i=1}{\overset{N}{}}\left(\frac{\widehat{𝐩}_i^2}{2m^{}}+\frac{m^{}\omega _0^2𝐫_i^2}{2}\right)+\frac{1}{2}\underset{ij=1}{\overset{N}{}}\frac{e^2}{|𝐫_i𝐫_j|}$$
(1)
($`N=3`$) commutes with operators of the total angular momentum $`\widehat{L}_z^{tot}`$, (squared) total spin $`\widehat{𝐒}_{tot}^2`$ and projection of the total spin $`\widehat{S}_\zeta ^{tot}`$ on some ($`\zeta `$-) axis (not necessarily coinciding with the $`z`$-axis). This gives three conserving quantum numbers $`L_{tot}L_z^{tot}`$, $`S_{tot}`$ and $`S_\zeta ^{tot}`$. No magnetic field is assumed to be applied to the system.

### B Basis set of single-particle states

A complete set of single-particle solutions of the problem

$$\varphi _{nls}(𝐫,\sigma )=\phi _{nl}(𝐫)\chi _s(\sigma )$$
(2)
is the product of the Fock-Darwin orbitals

$$\phi _{nl}(𝐫)=\frac{1}{l_0}\sqrt{\frac{n!}{\pi (n+|l|)!}}\left(\frac{r}{l_0}\right)^{|l|}e^{il\theta r^2/2l_0^2}L_n^{|l|}(r^2/l_0^2)$$
(3)
and the spin functions $`\chi _s(\sigma )`$. Here $`l_0=\sqrt{\mathrm{}/m^{}\omega _0}`$ is the oscillator length, and $`(n,l,s)`$ are the radial, asimutal (angular momentum) and spin quantum numbers of the single-particle problem ($`n0`$ and $`l`$ are integer, $`s=\pm 1/2`$). All the single-particle states (2) can be ordered and enumerated, e.g. $`\varphi _1(nls)_1=(0,0,)`$, $`\varphi _2=(0,0,)`$, $`\varphi _3=(0,1,)`$, etc. The energy of the states (2) does not depend on spins,

$$E_{nls}=\mathrm{}\omega _0(2n+|l|+1).$$
(4)
### C Basis set of many-particle states

A complete set of many-particle states $`\mathrm{\Psi }_u`$, $`u=1,2,\mathrm{}`$ is formed by placing particles in different single-particle states, e.g. $`\mathrm{\Psi }_1=|\varphi _1\varphi _2\varphi _3`$, $`\mathrm{\Psi }_2=|\varphi _1\varphi _2\varphi _4`$, $`\mathrm{}`$, where $`|\varphi _\alpha \varphi _\beta \varphi _\gamma `$ are Slater determinants

$$|\varphi _\alpha \varphi _\beta \varphi _\gamma =\frac{1}{\sqrt{3!}}det\left|\begin{array}{ccc}\varphi _\alpha (\xi _1)& \varphi _\beta (\xi _1)& \varphi _\gamma (\xi _1)\\ \varphi _\alpha (\xi _2)& \varphi _\beta (\xi _2)& \varphi _\gamma (\xi _2)\\ \varphi _\alpha (\xi _3)& \varphi _\beta (\xi _3)& \varphi _\gamma (\xi _3)\end{array}\right|$$
(5)
and $`\xi _i=(𝐫_i,\sigma _i)`$. All the many-particle states $`\mathrm{\Psi }_u`$ can be also arranged, e.g. in order of increasing of their total single-particle energy

$$E_u^{sp}=E_{(nls)_\alpha }+E_{(nls)_\beta }+E_{(nls)_\gamma },$$
(6)
and enumerated.

### D Solution of the Schrödinger equation

Expanding the many-body wave function in a complete set of many-particle states,

$$\mathrm{\Psi }(\xi _1,\xi _2,\xi _3)=\underset{u}{}C_u\mathrm{\Psi }_u(\xi _1,\xi _2,\xi _3),$$
(7)
I get the Schrödinger equation in the matrix form,

$$\underset{u^{}}{}(H_{uu^{}}E\delta _{uu^{}})C_u^{}=0.$$
(8)
The conservation of the total angular momentum $`L_{tot}`$ and the projection of the total spin $`S_\zeta ^{tot}`$ allows one to chose the many-body states for the expansion (7) under additional constraints

$$\underset{i=1}{\overset{N}{}}l_i=L_{tot},\underset{i=1}{\overset{N}{}}s_i=S_\zeta ^{tot}.$$
(9)
This reduces the size of the matrix in (8) and facilitates calculations.

Numerically diagonalizing the eigenvalue problem (8) I get a set of energy levels

$$E_{L_{tot},S_\zeta ^{tot},m}=\mathrm{}\omega _0_{L_{tot},S_\zeta ^{tot},m}(\lambda ),$$
(10)
and corresponding eigenfunctions

$$\mathrm{\Psi }_{L_{tot},S_\zeta ^{tot},m}=\underset{u}{}C_u^{L_{tot},S_\zeta ^{tot},m}(\lambda )\mathrm{\Psi }_u,$$
(11)
as a function of the interaction parameter $`\lambda =l_0/a_B`$. The number $`m=1,2,\mathrm{}`$ enumerates the energy levels of the system in the subspace of levels with given $`L_{tot}`$ and $`S_\zeta ^{tot}`$. After the diagonalization problem is solved, the eigenvalues of the total spin are calculated for each level $`m`$ from

$$S_{tot}(S_{tot}+1)=\mathrm{\Psi }_{L_{tot},S_\zeta ^{tot},m}|\widehat{𝐒}_{tot}^2|\mathrm{\Psi }_{L_{tot},S_\zeta ^{tot},m}.$$
(12)
All the matrix elements of the Hamiltonian $`H_{uu^{}}`$ and of the operator $`(\widehat{𝐒}_{tot}^2)_{uu^{}}`$ are calculated analytically.

All the energy levels with non-zero $`L_{tot}`$ and $`S_\zeta ^{tot}`$ are degenerate,

$$E_{L_{tot},S_\zeta ^{tot}}=E_{L_{tot},S_\zeta ^{tot}}=E_{L_{tot},S_\zeta ^{tot}}=E_{L_{tot},S_\zeta ^{tot}}.$$
(13)
Presenting below results for the energy of the states $`(L_{tot},S_\zeta ^{tot})`$, I omit the corresponding signs \[for instance, $`(1,1/2)`$ stands for $`(\pm 1,\pm 1/2)`$ with all possible combinations of signs\]. Degeneracy of levels are calculated accounting for (13).

### E Properties of the states and the heat capacity

After the Schrödinger problem is solved and all the energy levels and the eigenfunctions are found, I calculate the density of spin-up and spin-down polarized electrons in the states $`(L_{tot},S_\zeta ^{tot},m)`$, and the corresponding pair-correlation functions. These quantities are calculated as averages of the operators

$$\widehat{n}_\sigma (𝐫)=\underset{i=1}{\overset{N}{}}\delta (𝐫𝐫_i)\delta _{\sigma \sigma _i}$$
(14)
and

$$\widehat{P}_{\sigma \sigma ^{}}(𝐫,𝐫^{})=\underset{i=1}{\overset{N}{}}\underset{j=1,i}{\overset{N}{}}\delta (𝐫𝐫_i)\delta (𝐫^{}𝐫_j)\delta _{\sigma \sigma _i}\delta _{\sigma ^{}\sigma _j}$$
(15)
with the eigenfunctions $`\mathrm{\Psi }_{L_{tot},S_\zeta ^{tot},m}`$. All the matrix elements of the operators (14) and (15) are calculated analytically.

As the method offers an opportunity to find all the energy levels of the system, one can also calculate thermodynamic properties of the dots. I calculate the heat capacity as $`C_\lambda =(\overline{E}/T)_\lambda `$, where

$$\overline{E}\overline{E}(\lambda ,T)=\frac{_nE_n(\lambda )e^{E_n(\lambda )/T}}{_ne^{E_n(\lambda )/T}},$$
(16)
$`T`$ is the temperature, and the sum is taken over all (low-lying) energy levels accounting for their degeneracies.

### F Convergency of the method

The number of all many-particle states in the problem is infinite, and the size of the matrix $`H_{uu^{}}`$ in Eq. (8) is infinite too. To perform practical calculations I restrict the number of many-particle states in the expansion (7) so that the total single-particle energy (6) of the involved many-body states is smaller than some threshold value $`E_{th}`$, $`E_u^{sp}E_{th}`$. The larger the threshold energy $`E_{th}`$, the broader the range of $`\lambda `$ in which results are convergent and reliable. Typically, less than 1000 many-particle states were sufficient for all the calculations presented below.

Convergency of the method is illustrated on Figure 1, where the energy $`E_{(1,1/2)}`$ of the lowest state ($`m=1`$) with $`(L_{tot},S_{tot})=(1,1/2)`$ is shown as a function of $`\lambda =l_0/a_B`$ for increasing threshold energy $`E_{th}`$. The curves are labeled by $`E_{th}`$ and the number of many-body quantum states $`N_{mbs}`$ involved in the expansion (7). One sees that including about 1000 many-body states leads to very accurate results for the energy at $`\lambda 20`$. Notice that below I present results for the energy in the interval $`\lambda 10`$, where the method is practically exact: at $`\lambda =10`$ I found that $`E_{(1,1/2)}/\mathrm{}\omega _0=17.627891`$ at $`N_{mbs}=1024`$, and $`17.627974`$ at $`N_{mbs}=549`$. The difference comprises $`4.710^4`$ %.

## III Results

All the lengths in this Section are measured in units $`l_0`$, all the energies – in units $`\mathrm{}\omega _0`$, the densities and the pair-correlation functions – in units $`(\pi l_0^2)^1`$ and $`(\pi l_0^2)^2`$ respectively.

### A Energy spectra

#### 1 Exact results

The interaction parameter in the problem

$$\lambda =\frac{l_0}{a_B}=\sqrt{\frac{e^2/a_B}{\mathrm{}\omega _0}}\frac{e^2}{\mathrm{}^{3/2}}$$
(17)
characterizes the relative strength of classical Coulomb ($`e^2`$) and quantization effects ($`\mathrm{}`$). The limit of small $`\lambda `$ corresponds to a weakly interacting system ($`e^20`$) and can be treated exactly. The ground state in this limit is realized in the configuration $`[(0,0,)(0,0,)(0,1,)]`$, i.e. $`(L_{tot},S_{tot})=(1,1/2)`$, with the energy

$$\underset{\lambda 0}{lim}E_{GS}/\mathrm{}\omega _0=4.$$
(18)
The opposite case $`\lambda \mathrm{}`$ corresponds to the purely classical limit ($`\mathrm{}0`$). In the classical ground state, electrons occupy the corners of an equilateral triangle , with the distance

$$R_{cl}=l_{cl}/3^{1/6}$$
(19)
from the origin. The ground state energy at $`\lambda =\mathrm{}`$ is

$$E_{GS}^{cl}=3^{5/3}ϵ_{cl}/2.$$
(20)
Here $`l_{cl}=(e^2/m^{}\omega _0^2)^{1/3}`$ and $`ϵ_{cl}=e^2/l_{cl}`$ are the classical length and energy units. So, in the classical limit

$$\underset{\lambda \mathrm{}}{lim}E_{GS}/\mathrm{}\omega _0=3^{5/3}\lambda ^{2/3}/2.$$
(21)
Equations (18) and (21) give asymptotes of the ground state energy at very small and very large $`\lambda `$.

At arbitrary $`\lambda `$ one needs numerical calculations. Figure 2 shows the low-lying energy levels of a three-electron parabolic quantum dot with the total angular momentum $`L_{tot}=1`$. Shown are only the states which start from $`E/\mathrm{}\omega _06`$ at $`\lambda =0`$. The lowest-energy state (the ground state in the subspace of levels with $`L_{tot}=1`$) corresponds (in the limit $`\lambda 0`$) to the configuration $`[(0,0,)(0,0,)(0,1,)]`$, and has the total spin $`S_{tot}=1/2`$. This state is four-fold degenerate ($`L_{tot}=\pm 1/2`$, $`S_\zeta ^{tot}=\pm 1/2`$).

Figure 3 shows the low-lying energy levels with the total angular momentum $`L_{tot}=0`$. Shown are only the states which start from $`E/\mathrm{}\omega _07`$ at $`\lambda =0`$. The lowest-energy state has the total spin $`S_{tot}=3/2`$ and four-fold degeneracy ($`S_\zeta ^{tot}=\pm 3/2,\pm 1/2`$). In the limit $`\lambda 0`$ the state with the full spin polarization $`(S_{tot}=3/2,S_\zeta ^{tot}=+3/2)`$ corresponds to the configuration $`[(0,1,)(0,0,)(0,1,)]`$. The state with a partial spin polarization $`(S_{tot}=3/2,S_\zeta ^{tot}=+1/2)`$ corresponds in the limit $`\lambda 0`$ to the configuration $`(\mathrm{\Psi }_1+\mathrm{\Psi }_2+\mathrm{\Psi }_3)/\sqrt{3}`$, where

$`\mathrm{\Psi }_1`$ $`=`$ $`[(0,1,)(0,0,)(0,1,)],`$ (22)
$`\mathrm{\Psi }_2`$ $`=`$ $`[(0,1,)(0,0,)(0,1,)],`$ (23)
$`\mathrm{\Psi }_3`$ $`=`$ $`[(0,1,)(0,0,)(0,1,)].`$ (24)
I performed similar calculations for $`L_{tot}`$ from 0 to 9 and for all total-spin states $`S_{tot}=3/2`$ and 1/2. Results for $`L_{tot}`$ from 0 to 2 are shown in Figure 4. Only the lowest-energy levels ($`m=1`$) for each pair of numbers $`(L_{tot},S_{tot})`$ are shown in the Figure \[this means that, say, a (1,1/2)-level with $`m>1`$ (not shown in the Figure) may have the lower energy than the exhibited level $`(2,3/2)`$ with $`m=1`$\]. At some critical value of $`\lambda `$ ($`\lambda =\lambda _c=4.343`$) one observes a crossing of the two lowest-energy levels $`(1,1/2)`$ and $`(0,3/2)`$ (more clearly seen in Figure 5 where the energy difference $`E_{(0,3/2)}E_{(1,1/2)}`$ is plotted versus $`\lambda `$). At the critical point the total spin of the system in the ground state changes from $`S_{tot}=1/2`$ at $`\lambda <\lambda _c`$ to $`S_{tot}=3/2`$ at $`\lambda >\lambda _c`$. Near the critical point the gap between the ground and the first excited states behaves as

$$|E_{(0,3/2)}E_{(1,1/2)}|/\mathrm{}\omega _0=0.02766|\lambda \lambda _c|,$$
(25)
with a jump of the derivative of the ground state energy with respect to $`\lambda `$. At large $`\lambda `$ (more exactly, at $`\lambda =10`$) the energy difference is $`E_{(0,3/2)}E_{(1,1/2)}0.0416\mathrm{}\omega _0`$.

In Table I exact results for the energies of the states (1,1/2) and (0,3/2) are compared with QMC results from Ref. . One sees that the accuracy of the QMC results  is in general very high, but the errors are not always small (see e.g. $`\lambda =10`$) compared to the difference between the energies of the ground and excited states.

#### 2 Approximations

The energy of the states $`(1,1/2)`$ and $`(0,3/2)`$ can be approximated, in the interval $`0\lambda 10`$, by the formula

$$E=E_{GS}^{cl}+ϵ_{cl}\left(AX+\sqrt{B^2+C^2X^2}B\right),$$
(26)
where $`E_{GS}^{cl}`$ is the classical ground state energy (20), $`X=\mathrm{}\omega _0/ϵ_{cl}`$, and the numbers $`A,B,C`$ for the two considered states are

$$(A,B,C)_{(1,1/2)}=(3.11536,2.93076,0.917954),$$
(27)
$$(A,B,C)_{(0,3/2)}=(2.84171,2.44529,2.13633).$$
(28)
For the state $`(1,1/2)`$ the difference between the exact energy and the approximation (26)–(27) is about 0.83% at $`\lambda =0`$, does not exceed 0.22% at $`0.05\lambda 10`$, and tends to zero with growing $`\lambda `$. For the state $`(0,3/2)`$ the difference between the exact solution and the approximation is smaller than 0.44% in the whole range of $`\lambda `$. It should be noted however, that the difference between the energies of the two states $`E_{(0,3/2)}E_{(1,1/2)}`$ is reproduced by the approximate formulas (26)–(28) with a substantially worse accuracy.

### B Heat capacity

Figure 6 exhibits the calculated low-temperature heat capacity $`C_\lambda `$ as a function of $`T`$ and $`\lambda `$. About 30 lowest-energy levels for each $`L_{tot}`$ from 0 to 9, with corresponding degeneracies, were taken into account in this calculation. A pronounced peak related to the gap between the ground and the first excited state can be clearly seen in this Figure. The value of the peak temperature $`T_p(\lambda )`$ depends on $`\lambda `$ as $`|E_{(0,3/2)}E_{(1,1/2)}|`$ (compare to Figure 5), and disappears at the critical point $`\lambda =\lambda _c`$. The most dramatic variations of the heat capacity are the case in the range $`kT0.1\mathrm{}\omega _0`$, which corresponds, at a typical confinement of GaAs quantum dots ($`\mathrm{}\omega _03`$ meV), to a few-K temperature scale.

### C Electron density and correlations

Due to rotational symmetry of the Hamiltonian (1) the density $`n_\sigma ^{(L_{tot},S_{tot})}(r,\theta )`$ of spin-up and spin-down polarized electrons in the quantum-mechanical states $`(L_{tot},S_{tot})`$ does not depend on the angular coordinate $`\theta `$, and are shown below as a function of $`r`$ only. The pair-correlation functions $`P_{\sigma \sigma ^{}}(𝐫,𝐫^{})`$ are plotted as a function of $`𝐫/l_0`$, for all orientations of spins, at the second coordinate $`𝐫^{}`$ being fixed at the classical distance (19) from the origin, $`𝐫^{}=(0,R_{cl})`$ (the second subscript corresponds to the spin of a fixed electron).

#### 1 The state $`(L_{tot},S_{tot})=(0,3/2)`$

The total density of electrons $`n^{(0,3/2)}(r)=n_{}^{(0,3/2)}(r)+n_{}^{(0,3/2)}(r)`$ in the state $`(L_{tot},S_{tot})=(0,3/2)`$ at a few values of the interaction parameter $`\lambda `$ is shown in Figure 7. The function $`n^{(0,3/2)}(r)`$ also determines the densities of spin-up and spin-down polarized electrons: in the state with the total spin projection $`S_\zeta ^{tot}=+3/2`$ the density of spin-up electrons coincides with $`n^{(0,3/2)}(r)`$, while the density of spin-down electrons is zero; in the $`S_\zeta ^{tot}=+1/2`$ state one has $`n_{}^{(0,3/2,+1/2)}(r)=\frac{2}{3}n^{(0,3/2)}(r)`$, and $`n_{}^{(0,3/2,+1/2)}(r)=\frac{1}{3}n^{(0,3/2)}(r)`$. One sees that at all $`\lambda `$ maxima of the electron density lie at a finite distance from the origin. At $`\lambda 1`$ they are very close to the classical radii (19), shown by triangles on the Figure; at $`\lambda 1`$ (weak Coulomb repulsion) they are at even larger $`r`$, due to the exchange repulsion.

Figure 8 exhibits the pair-correlation function $`P_{}(𝐫,𝐫^{})`$ in the state $`(L_{tot},S_{tot},S_\zeta ^{tot})=(0,3/2,+3/2)`$ (three other functions in this state obviously vanish, $`P_{}=P_{}=P_{}=0`$; in the state with $`S_\zeta ^{tot}=+1/2`$ one has $`P_{,,}^{(0,3/2,+1/2)}=\frac{1}{3}P_{}^{(0,3/2,+3/2)}`$, and $`P_{}^{(0,3/2,+1/2)}=0`$). The interaction parameter $`\lambda `$ assumes the values 0.1, 2, 4, and 8, from up to down. At small $`\lambda `$ electron-electron interaction is weak, and the pair-correlation function has a form of a single peak centered opposite to the fixed electron. With growing $`\lambda `$ this peak is splitted onto two ones, and this splitting becomes very pronounced at strong Coulomb interaction ($`\lambda 4`$).

The internal structure of the state $`(0,3/2)`$ thus corresponds to the angle-averaged classical configuration of an equilateral triangle (see the inset to Figure 3). This structure is highly symmetric and “rigid”: the ratio of the sides of the triangle remains unchanged when the curvature $`K`$ of the confiment potential varies ($`K\lambda ^4`$). This state is a quantum-dot analog of the Wigner solid (a Wigner molecule).

#### 2 The state $`(L_{tot},S_{tot})=(1,1/2)`$

In the state $`(1,1/2)`$ the spatial distribution of electrons is less trivial. Now we have two sorts of particles: two electrons are polarized up, and one electron is polarized down. Figure 9 exhibits the total electron density (spin-up plus spin-down). One sees that at small $`\lambda `$ electrons behave as non- or weakly interacting particles (a Fermi-liquid-type state), forming the structure with maximum of the electron density at $`r=0`$. Such a picture is the case up to $`\lambda 2`$, when a weak minimum of the density at $`r=0`$ appears. At even larger $`\lambda `$ the influence of electron-electron interaction becomes more important: the density of electrons qualitatively looks like in the state (0,3/2), with a minimum at $`r=0`$ and maxima close to the classical radii (19).

Additional and even more interesting information can be extracted from Figures 10 and 11, which show separately the densities of spin-up and spin-down polarized electrons. One sees that at small $`\lambda `$ the one spin-down electron occupies the center of the dot, while the two spin-up electrons rotate around the center with a maximum of the density at a finite distance from the origin. Such a situation is a peculiar quantum-mechanical feature: it is not encountered in the classical picture. With the growing $`\lambda `$ (electron-electron interaction increases) the two spin-up electrons push the spin-down electron out from the center, but the structure “one (spin-down) electron is essentially closer to the center, two (spin-up) electrons rotate around” conserves up to $`\lambda 2`$: the density of the spin-up electrons has a clear maximum at a finite distance from the origin, while the density of spin-down electron still maximal at $`r=0`$. At even larger $`\lambda `$ ($`4`$) (stronger electron-electron interaction) the density maximum of the spin-down electron is shifted to a finite $`r`$, but at any $`\lambda `$ it is closer to the origin, than the density maximum of the spin-up electrons.

These features can be also seen in Figures 12, 13, and 14, which exhibit the pair-correlation functions $`P_{}`$, $`P_{}`$, and $`P_{}`$ in the state $`(L_{tot},S_{tot},S_\zeta ^{tot})=(1,1/2,+1/2)`$ ($`P_{}=0`$ in this state). Compare for instance Figures 12 ($`P_{}`$) and 13 ($`P_{}`$). In both cases a spin-up electron is fixed at the classical distance from the origin. Let $`\lambda =2`$ (the second row of plots). One sees that the maximum of the pair-correlation function is about two times closer to the center of the dot for the spin-down electron (Figure 13) than for the spin-up electron (Figure 12). At $`\lambda =4`$ this difference is less pronounced but can also be seen. In Figure 13 one also sees that in the limit of weak Coulomb interaction $`\lambda 1`$ the spin-down electron is localized in the center, in agreement with the above analysis of the density plots.

The internal structure of the state $`(1,1/2)`$ thus corresponds to an angle-averaged configuration of an isosceles triangle, with two spin-up electrons at the base corners and one spin-down electron at the top of the triangle. This structure is less symmetric than that of the $`(0,3/2)`$ state and “soft”: the ratio of the sides varies with $`\lambda `$, changing from 1/2 at $`\lambda =0`$ to 1 at $`\lambda =\mathrm{}`$ (see the insets to Figure 2). This state is of a Fermi-liquid type (Fermi-gas at $`\lambda 0`$).

#### 3 Reconstruction of the ground state

Now, we can understand the physical reason of the transition $`(1,1/2)(0,3/2)`$ at the varying parameter $`\lambda `$. Consider what happens with the ground state of the system, when the curvature $`K\omega _0^2\lambda ^4`$ of the confinement potential varies from small (the limit of strong Coulomb interaction $`\lambda \mathrm{}`$) to large values (the weak Coulomb interaction regime). At small $`K`$ the quantization effects are negligible, $`\mathrm{}\omega _0/ϵ_{cl}=\lambda ^{2/3}1`$, electrons are at a large (compared to $`l_0`$) distance from each other, and form a quasi-classical equilateral-triangle structure. In this highly-symmetric structure all electrons should be equivalent (have the same spin), therefore the total spin of the dot in this limit is $`S_{tot}=3/2`$. Increasing the curvature reduces the area of the triangle. Its form however first remains unchanged. Further increase of the curvature costs energy, and the system is reconstructed, at $`\lambda =\lambda _c`$, to another ground state with a more compact, “soft” isosceles-triangle structure. In this less symmetric structure one electron should differ from two others, therefore the transition to the new ground state is accompanied by the change of the total spin $`S_{tot}1/2`$. Further increase of the curvature changes the ratio of sides of the isosceles triangle, but not its symmetry.

Exactly at the transition point $`\lambda =\lambda _c`$ the physical properties of the dot change very sharply. Figure 15 shows the total density of electrons $`n_e(r)`$ at $`\lambda =\lambda _c`$ in the states $`(0,3/2)`$ and $`(1,1/2)`$. When the system passes from the $`(0,3/2)`$ to the (1,1/2) state, electrons are pushed towards the center of the dot with a 50% increase of the density at the point $`r=0`$. Figure 16 shows the area of the dot

$$A=\frac{1}{N}𝑑𝐫\pi r^2n_e(r)=\frac{\pi }{N}\mathrm{\Psi }_{GS}|\underset{i}{}r_i^2|\mathrm{\Psi }_{GS}$$
(29)
\[$`\mathrm{\Psi }_{GS}`$ is the ground-state wave function\] versus the curvature $`K\lambda ^4`$ near the critical point $`\lambda =\lambda _c`$. As the curvature of the confinement potential can be treated as a “pressure” acting on electrons of the dot from the confining potential, Figure 16 can be considered as a “volume”–“pressure” diagram. One sees that increasing the pressure leads to a discontinuous jump of the volume (with a $`\delta `$-like peculiarity in the compressibility) at the critical point $`\lambda =\lambda _c`$. In a real system the transition shown in Figure 16 may happen with a hysteresis.

## IV Concluding remarks

The transition $`(0,3/2)(1,1/2)`$ in the quantum-dot lithium is very similar to the Fermi-liquid – Wigner-solid transition in an infinite 2DES . This becomes evident if to plot results of quantum-dot and 2DES calculations in the form of an expansion in powers of $`\mathrm{}`$: energy in units $`ϵ_{cl}`$ vs $`\lambda ^{2/3}`$ in dots, and energy in units $`e^2\sqrt{n_s}`$ vs $`r_s^{1/2}`$ in 2DES; here $`r_s=1/\sqrt{\pi n_s}a_B`$. In such coordinates the ground-state-energy curves, both in dots and in 2DES, look very similarly: the Fermi-liquid and the Wigner-solid energies are smooth, almost linear functions \[for dots see Eq. (26)\], intersecting each other at some value of the interaction parameter. In the regime of strong interaction the fully spin-polarized Wigner solid is the ground state in both the 2DES and the dot; in the regime of weak interaction the unpolarized (partly-polarized in three-electron dots) Fermi-liquid state is the ground state of both systems. The transition $`(0,3/2)(1,1/2)`$ in the quantum-dot lithium is thus an analog (or a precursor) of the Fermi-liquid–Wigner-solid transition in an infinite 2DES .

The transition $`(1,1/2)(0,3/2)`$ should be observable in many experiments. It should manifest itself in any thermodynamic quantity. The difference in the ground-state total spin $`S_{tot}`$ should be also seen in the Zeeman and spin splitting of levels in magnetic field, both parallel and perpendicular to the plane of 2DES, as well as in Kondo-effect experiments. The structure of levels could be also studied by Raman spectroscopy.

The method of the paper can be used for studying systems with more particles and/or in a non-parabolic confinement potential . It can also be used for investigating other properties of the system, for instance, the influence of impurities, or response of the dot to external fields. It is seen already now, for instance, that an asymmetrically located impurity will qualitatively differently affect the ground state of the dot at $`\lambda <\lambda _c`$ and at $`\lambda >\lambda _c`$: in the former (the latter) case the ground state is degenerate (non-degenerate) with respect to $`L_{tot}`$, and the impurity will result in a splitting (a shift) of the ground state level.

To summarize, I have performed a complete theoretical study of a system of three Coulomb-interacting electrons in a parabolic confining potential, and investigated in detail physical properties and the origin of the Fermi liquid – Wigner solid transition in the ground state of the three-electron parabolic quantum dot.

###### Acknowledgements.

The work was supported by the Sonderforschungsbereich SFB 484, University of Augsburg. I thank Klaus Ziegler, Ulrich Eckern, Vladimir Sablikov, Teun Klapwijk and Miodrag Kulic for useful discussions, as well as referees of the paper for useful comments.