Theoretical issues in the accurate computation of the electron-phonon interaction contribution to the total energy

Fuente: arXiv
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Autores principales: Paul, Shilpa, Gururajan, M. P., Bhattacharya, Amrita, Prasanna, T. R. S.
Formato: Preprint
Publicado: 2023
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author Paul, Shilpa
Gururajan, M. P.
Bhattacharya, Amrita
Prasanna, T. R. S.
author_facet Paul, Shilpa
Gururajan, M. P.
Bhattacharya, Amrita
Prasanna, T. R. S.
contents We report the computation of the Standard Hamiltonian of a coupled electron-phonon system by accurately computing the electron-phonon interaction (EPI) contribution to the total energy. This gives the most accurate ab initio total energy till date. However, our results show that the per-atom EPI energy is unit-cell-size dependent due to the partial-Fan-Migdal term that arises from the antisymmetric nature of the crystal wavefunction. Due to this, only energy differences between polytypes, in supercells with identical number of atoms, are meaningful, rather than per-atom total energy. This violates our understanding of Quantum Mechanics applied to periodic solids and raises serious theoretical questions. In his original (1951) paper, Fan suggested, without specifying any reason, that second-order perturbation theory applied to the whole crystal is of questionable validity. Our results support Fan's suggestion for the reason that the partial-FM term makes the per-atom total energy unit-cell-size dependent. This leads to a new fundamental problem in condensed matter physics, viz. second-order perturbation theory is invalid for whole crystals, an entire class. It is essential to resolve this problem, especially because it causes the standard Hamiltonian, the starting point of EPI studies and the most accurate ab initio total energy, to be of questionable validity.
format Preprint
id arxiv_https___arxiv_org_abs_2309_04279
institution arXiv
publishDate 2023
record_format arxiv
spellingShingle Theoretical issues in the accurate computation of the electron-phonon interaction contribution to the total energy
Paul, Shilpa
Gururajan, M. P.
Bhattacharya, Amrita
Prasanna, T. R. S.
Materials Science
We report the computation of the Standard Hamiltonian of a coupled electron-phonon system by accurately computing the electron-phonon interaction (EPI) contribution to the total energy. This gives the most accurate ab initio total energy till date. However, our results show that the per-atom EPI energy is unit-cell-size dependent due to the partial-Fan-Migdal term that arises from the antisymmetric nature of the crystal wavefunction. Due to this, only energy differences between polytypes, in supercells with identical number of atoms, are meaningful, rather than per-atom total energy. This violates our understanding of Quantum Mechanics applied to periodic solids and raises serious theoretical questions. In his original (1951) paper, Fan suggested, without specifying any reason, that second-order perturbation theory applied to the whole crystal is of questionable validity. Our results support Fan's suggestion for the reason that the partial-FM term makes the per-atom total energy unit-cell-size dependent. This leads to a new fundamental problem in condensed matter physics, viz. second-order perturbation theory is invalid for whole crystals, an entire class. It is essential to resolve this problem, especially because it causes the standard Hamiltonian, the starting point of EPI studies and the most accurate ab initio total energy, to be of questionable validity.
title Theoretical issues in the accurate computation of the electron-phonon interaction contribution to the total energy
topic Materials Science
url https://arxiv.org/abs/2309.04279