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Physical review. B, Condensed matter

Temperature-dependent free-electron susceptibility for one, two, and three dimensions

Jae Gil Kim, Yoon-Hyuck Sean Choi, Eok Kyun Lee, Soonchil Lee

Published Feb 1, 1999• 8 citations
Publisher

Abstract

The analytical forms of free-electron susceptibilities ${\ensuremath{\chi}}_{d}(q)$ and their range functions ${\ensuremath{\chi}}_{d}(r)$ are derived at nonzero temperature starting from the Green's function representation by properly evaluating the contributions from the poles of free-electron temperature Green's function for each dimension $d=1,$ 2, and 3. The present formalism produces not only ${\ensuremath{\chi}}_{d}(q)$ and ${\ensuremath{\chi}}_{d}(r)$ which show more accurate temperature-dependent behavior than our previous results for $d=1$ and 3, but also temperature-dependent two-dimensional ${\ensuremath{\chi}}_{2}(q)$ and ${\ensuremath{\chi}}_{2}(r)$ for a wide range of temperature. Our analytical results show that irrespective of dimension, the singular behavior of ${\ensuremath{\chi}}_{d}(q)$ at $q=\ifmmode\pm\else\textpm\fi{}{2k}_{F}$ becomes suppressed at nonzero temperature as the singular points transit to complex wave vectors ${2k}_{0}^{\ifmmode\pm\else\textpm\fi{}},$ and this transition causes ${\ensuremath{\chi}}_{d}(r)$ to be exponentially damped with common damping factor ${e}^{\ensuremath{-}2{\ensuremath{\eta}}_{0}\mathrm{sin}{\ensuremath{\varphi}}_{r}{k}_{F}r}\ensuremath{\sim}{e}^{\ensuremath{-}\ensuremath{\pi}{T}^{\ensuremath{'}}{k}_{F}r}$ for low enough temperature, where the exponent of the damping factor corresponds to an imaginary part of wave vectors ${2k}_{0}^{\ifmmode\pm\else\textpm\fi{}}.$ We also show that the causality relation of the response function is essential in understanding the correct behavior of ${\ensuremath{\chi}}_{d}(q)$ and ${\ensuremath{\chi}}_{d}(r)$ for all dimensions.

DOI
10.1103/physrevb.59.3661

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The analytical structure of the wave-number-dependent magnetic susceptibility $\ensuremath{\chi}(\stackrel{\ensuremath{\rightarrow}}{\mathrm{k}})$ is studied at small wave number $\stackrel{\ensuremath{\rightarrow}}{\mathrm{k}}$ and low temperature. It is found to exhibit a nonanalytic behavior in contrast to commonly assumed forms for $\ensuremath{\chi}(\stackrel{\ensuremath{\rightarrow}}{\mathrm{k}})$ of interacting systems. The importance and implications of these results are discussed for the cases of short-range point interactions and long-range Coulomb interactions.
Description of electron correlation is crucial to chemical accuracy in quantum chemical calculations. However, the interaction of electrons in a system is an insoluble many-body problem. Constructing approximations to describe electron correlation is a challenging task, but there has been success in the quantum chemistry community using wavefunction methods and density functional theory. However, there are still challenges to be overcome in areas such as theoretical solid state chemistry, which requires description of large systems and the use of finite temperature. Large system sizes and finite temperature can be difficult to treat solely with the currently available methods. Therefore, a new class of methods, based on the temperature-dependent Green's function, is implemented and explored. This thesis is toward investigating the use of temperature-dependent Green's functions for ab-initio quantum chemistry. That is, we are treating a quantum chemical Hamiltonian with realistic electron interactions. While this formalism has been applied to model systems in the condensed matter community, its has been used much less by the quantum chemistry community. Therefore, the numerical behavior and accuracy of Green's function methods for quantum chemical calculations is relatively unknown. This work investigates the ability of the temperature-dependent Green's function, which is an ensemble formalism, to give access to temperature dependent thermodynamic quantities such as free energy and entropy when calculated in a second-order and perturbative manner (GF2). We find that this method is able to give good accuracy for lower temperatures and excellent accuracy for higher temperatures for a molecular case and is able to qualitatively describe a simple model of a solid. The results of this work are presented in chapter 3. Although Green's functions have a clear connection with spectra at zero temperature, it is not straight forward to obtain spectra from the finite temperature Green's function, which is calculated on the imaginary frequency axis. Therefore, we must investigate methods to obtain spectral quantities in a consistent and reliable manner from the imaginary axis. Chapter 4 investigates several methods to do so and we compare our results with experimental and highly accurate benchmark data. We find that it is possible to obtain spectral quantities that can differ by several electron volts, even if the same level of theory is used to obtain the Green's function. This reiterates that finding a spectrum from the imaginary axis is nontrivial and that one must exercise caution when comparing spectral quantities that were calculated using different techniques, even if they are treated with the same theoretical accuracy. Accessing larger systems with the Green's function requires the use of quantum embedding. Quantum embedding describes nontrivial electron interaction between a highly accurate ``active space'' or ``impurity'' and a larger, lower level ``environment''. It is challenging to construct an impurity solver that is reliable at low temperatures. In chapter 5 of this work, we implement and test a temperature dependent configuration interaction impurity solver for quantum embedding. This solver can be used in quantum embedding schemes such as dynamical mean field theory and self-energy embedding theory for larger systems. Overall, this thesis has made progress toward using Green's functions for ab-initio quantum chemistry at finite temperature. Groundwork has been laid for using this formalism to calculate thermodynamics and spectra using a Green's function with realistic electron interactions and to explore quantum embedding using an impurity solver at low temperatures.
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We compute exactly the four coefficients ${C}_{0\ifmmode\pm\else\textpm\fi{}}$ and ${C}_{1\ifmmode\pm\else\textpm\fi{}}$ in the expansion ${\ensuremath{\beta}}^{\ensuremath{-}1}\ensuremath{\chi}={C}_{0\ifmmode\pm\else\textpm\fi{}}{|1\ensuremath{-}\frac{{T}_{c}}{T}|}^{\ensuremath{-}\frac{7}{4}}+{C}_{1\ifmmode\pm\else\textpm\fi{}}{|1\ensuremath{-}\frac{{T}_{c}}{T}|}^{\ensuremath{-}\frac{3}{4}}+O(1)$ for the susceptibility of the rectangular two-dimensional Ising model.
The modulation is analyzed from the analytical properties of zeros of the free fermionic partition function on the complex plane of wave numbers. It is shown how these properties are related to the oscillations of correlation functions. This approach can be used for analysis of phase transitions with local or nonlocal order parameters, as well as for the disorder lines. We find an infinite cascade of disorder lines at finite temperature in the quantum XYXYXY chain (equivalent to free fermions). The well-known ground-state factorization on the disorder line, and consequently disentanglement, is shown to follow directly from analytical properties of this model on the complex plane. From the quantum-classical correspondence the results for the chain are used to detect the disorder lines in several frustrated two-dimensional Ising models. The present formalism can be applied to other fermionic models in two and three spatial dimensions. In particular, we find the temperature-dependent Fermi wave vector of oscillations in the degenerate gas of three-dimensional fermions, which naturally leads in the limit $T\ensuremath{\rightarrow}0$ to the definition of the Fermi energy as the surface of quantum criticality. The modulation is a very common phenomenon, and it occurs in a large variety of models. The important point is that all these modulation transitions can be related to the complex zeros of partition functions, as done in the present study.