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arXiv:2203.02377 · The Journal of Chemical Physics

Complex analysis of divergent perturbation theory at finite temperature

Yi Sun, Hugh G. A. Burton

Published May 2, 2022• 1 citation
arXivHTMLPDF

Abstract

We investigate the convergence properties of finite-temperature perturbation theory by considering the mathematical structure of thermodynamic potentials using complex analysis. We discover that zeros of the partition function lead to poles in the internal energy and logarithmic singularities in the Helmholtz free energy that create divergent expansions in the canonical ensemble. Analyzing these zeros reveals that the radius of convergence increases at higher temperatures. In contrast, when the reference state is degenerate, these poles in the internal energy create a zero radius of convergence in the zero-temperature limit. Finally, by showing that the poles in the internal energy reduce to exceptional points in the zero-temperature limit, we unify the two main mathematical representations of quantum phase transitions.

DOI
10.1063/5.0091442

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We investigate the convergence properties of finite-temperature perturbation theory by considering the mathematical structure of thermodynamic potentials using complex analysis. We discover that zeros of the partition function lead to poles in the internal energy and logarithmic singularities in the Helmholtz free energy that create divergent expansions in the canonical ensemble. Analyzing these zeros reveals that the radius of convergence increases at higher temperatures. In contrast, when the reference state is degenerate, these poles in the internal energy create a zero radius of convergence in the zero-temperature limit. Finally, by showing that the poles in the internal energy reduce to exceptional points in the zero-temperature limit, we unify the two main mathematical representations of quantum phase transitions.
It is shown analytically and numerically that the finite-temperature many-body perturbation theory in the grand canonical ensemble has zero radius of convergence at zero temperature when the energy ordering or degree of degeneracy for the ground state changes with the perturbation strength. When the degeneracy of the reference state is partially or fully lifted at the first-order Hirschfelder-Certain degenerate perturbation theory, the second-order grand potential and internal energy diverge as $T\ensuremath{\rightarrow}0$. Contrary to earlier suggestions of renormalizability by the chemical potential $\ensuremath{\mu}$, this nonconvergence, first suspected by Kohn and Luttinger, is caused by the nonanalytic nature of the Boltzmann factor ${e}^{\ensuremath{-}E/{k}_{\text{B}}T}$ at T=0T=0T=0, also plaguing the canonical ensemble, which does not involve $\ensuremath{\mu}$. The finding reveals a fundamental flaw in perturbation theory, which is deeply rooted in the mathematical limitation of power-series expansions and is unlikely to be removed within its framework.
Benchmark data are presented for the zeroth- through third-order many-body perturbation corrections to the electronic Helmholtz energy, internal energy, and entropy in the canonical ensemble in a wide range of temperature. They are determined as numerical λ-derivatives of the respective quantities computed by thermal full configuration interaction with a perturbation-scaled Hamiltonian, H[over ̂]=H[over ̂]_{0}+λV[over ̂]. Sum-over-states analytical formulas for up to the third-order corrections to these properties are also derived as analytical λ-derivatives. These formulas, which are verified by exact numerical agreement with the benchmark data, are given in terms of the Hirschfelder-Certain degenerate perturbation energies and should be valid for both degenerate and nondegenerate reference states at any temperature down to zero. The results in the canonical ensemble are compared with the same in the grand canonical ensemble.
A comprehensive and detailed account is presented for the finite-temperature many-body perturbation theory for electrons that expands in power series all thermodynamic functions on an equal footing. Algebraic recursions in the style of the Rayleigh-Schrödinger perturbation theory are derived for the grand potential, chemical potential, internal energy, and entropy in the grand canonical ensemble and for the Helmholtz energy, internal energy, and entropy in the canonical ensemble, leading to their sum-over-states analytical formulas at any arbitrary order. For the grand canonical ensemble, these sum-over-states formulas are systematically transformed to sum-over-orbitals reduced analytical formulas by the quantum-field-theoretical techniques of normal-ordered second quantization and Feynman diagrams extended to finite temperature. It is found that the perturbation corrections to energies entering the recursions have to be treated as a nondiagonal matrix, whose off-diagonal elements are generally nonzero within a subspace spanned by degenerate Slater determinants. They give rise to a unique set of linked diagrams-renormalization diagrams-whose resolvent lines are displaced upward, which are distinct from the well-known anomalous diagrams of which one or more resolvent lines are erased. A linked-diagram theorem is introduced that proves the size-consistency of the finite-temperature many-body perturbation theory at any order. General-order algorithms implementing the recursions establish the convergence of the perturbation series toward the finite-temperature full-configuration-interaction limit unless the series diverges. The normal-ordered Hamiltonian at finite temperature sheds light on the relationship between the finite-temperature Hartree-Fock and first-order many-body perturbation theories.
We study the Bose-Einstein condensation phase transition in a weakly interacting gas through a perturbative analysis of finite systems. In both the grand canonical and the canonical ensembles, perturbation theory suffers from infrared divergences and cannot directly determine the transition temperature in the thermodynamic limit. However, in conjunction with finite-size scaling, perturbation theory provides a powerful calculation tool. Here we use this combination of perturbation theory and scaling to estimate a shift in the transition temperature in the canonical ensemble consistent with grand canonical calculations.
A finite-temperature many-body perturbation theory is presented, which expands in power series the electronic grand potential, chemical potential, internal energy, and entropy on an equal footing. Sum-over-states and sum-over-orbitals analytical formulas for the second-order perturbation corrections to these thermodynamic properties are obtained in a time-independent, nondiagrammatic, algebraic derivation, relying on the sum rules of the Hirschfelder–Certain degenerate perturbation energies in a degenerate subspace as well as nine algebraic identities for the zeroth-order thermal averages of one- through four-indexed quantities and products thereof. They reproduce numerically exactly the benchmark data obtained as the numerical derivatives of the thermal-full-configuration-interaction results for a wide range of temperatures.
Low-temperature expansion of Ising model has long been a topic of significant interest in condensed matter and statistical physics. In this paper we present new results of the coefficients in the low-temperature series of the Ising partition function on the square lattice, in the cases of a zero field and of an imaginary field $i(\ensuremath{\pi}/2){k}_{B}T$. The coefficients in the low-temperature series of the free energy in the thermodynamic limit are represented using the explicit expression of the density function of the Fisher zeros. The asymptotic behavior of the sequence of the coefficients when the order goes to infinity is determined exactly, for both the series of the free energy and of the partition function. Our analytic and numerical results demonstrate that the convergence radius of the sequence is dependent on the accumulation points of the Fisher zeros, which have the smallest modulus. In the zero field case this accumulation point is the physical critical point, while in the imaginary field case it corresponds to a nonphysical singularity. We further discuss the relation between the series coefficients and the energy state degeneracies, using the combinatorial expression of the coefficients and the subgraph expansion.