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Title: Finite-temperature second-order many-body perturbation and Hartree–Fock theories for one-dimensional solids: An application to Peierls and charge-density-wave transitions in conjugated polymers

Finite-temperature extensions of ab initio Gaussian-basis-set spin-restricted Hartree–Fock (HF) and second-order many-body perturbation (MP2) theories are implemented for infinitely extended, periodic, one-dimensional solids and applied to the Peierls and charge-density-wave (CDW) transitions in polyyne and all-trans polyacetylene. The HF theory predicts insulating CDW ground states for both systems in their equidistant structures at low temperatures. In the same structures, they turn metallic at high temperatures. Starting from the “dimerized” low-temperature equilibrium structures, the systems need even higher temperatures to undergo a Peierls transition, which is accompanied by geometric as well as electronic distortions from dimerized to non-dimerized forms. The conventional finite-temperature MP2 theory shows a sign of divergence in any phase at any nonzero temperature and is useless. The renormalized finite-temperature MP2 (MP2R) theory is divergent only near metallic electronic structures, but is well behaved elsewhere. MP2R also predicts CDW and Peierls transitions occurring at two different temperatures. The effect of electron correlation is primarily to lower the Peierls transition temperature.
Authors:
 [1] ;  [2] ;  [3] ;  [1] ;  [4]
  1. Department of Chemistry, University of Illinois at Urbana-Champaign, 600 South Mathews Avenue, Urbana, Illinois 61801 (United States)
  2. (China)
  3. Department of Physics, University of Illinois at Urbana-Champaign, 1100 West Green Street, Urbana, Illinois 61801 (United States)
  4. (Japan)
Publication Date:
OSTI Identifier:
22253636
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 140; Journal Issue: 2; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; 74 ATOMIC AND MOLECULAR PHYSICS; CHARGE DENSITY; DISTURBANCES; ELECTRON CORRELATION; ELECTRONIC STRUCTURE; GROUND STATES; MANY-BODY PROBLEM; ONE-DIMENSIONAL CALCULATIONS; PERIODICITY; PERTURBATION THEORY; POLYMERS; RENORMALIZATION; SOLIDS; TRANSITION TEMPERATURE