Strong electron correlation from partition density functional theory

Author:

Shi Yi1ORCID,Shi Yuming2ORCID,Wasserman Adam12ORCID

Affiliation:

1. Department of Chemistry, Purdue University 1 , West Lafayette, Indiana 47907, USA

2. Department of Physics and Astronomy, Purdue University 2 , West Lafayette, Indiana 47907, USA

Abstract

Standard approximations for the exchange–correlation functional in Kohn–Sham density functional theory (KS-DFT) typically lead to unacceptably large errors when applied to strongly correlated electronic systems. Partition-DFT (PDFT) is a formally exact reformulation of KS-DFT in which the ground-state density and energy of a system are obtained through self-consistent calculations on isolated fragments, with a partition energy representing inter-fragment interactions. Here, we show how typical errors of the local density approximation (LDA) in KS-DFT can be largely suppressed through a simple approximation, the multi-fragment overlap approximation (MFOA), for the partition energy in PDFT. Our method is illustrated on simple models of one-dimensional strongly correlated linear hydrogen chains. The MFOA, when used in combination with the LDA for the fragments, improves LDA dissociation curves of hydrogen chains and produces results that are comparable to those of spin-unrestricted LDA, but without breaking the spin symmetry. MFOA also induces a correction to the LDA electron density that partially captures the correct density dimerization in strongly correlated hydrogen chains. Moreover, with an additional correction to the partition energy that is specific to the one-dimensional LDA, the approximation is shown to produce dissociation energies in quantitative agreement with calculations based on the density matrix renormalization group method.

Funder

National Science Foundation

American Chemical Society Petroleum Research Fund

Publisher

AIP Publishing

Subject

Physical and Theoretical Chemistry,General Physics and Astronomy

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