Distinguishing artificial and essential symmetry breaking in a single determinant: approach and application to the C60, C36, and C20 fullerenes

Lee, Joonho; Head-Gordon, Martin

doi:10.1039/c8cp07613h

Title: Distinguishing artificial and essential symmetry breaking in a single determinant: approach and application to the C₆₀, C₃₆, and C₂₀ fullerenes

Journal Article · 06 February 2019 · Physical Chemistry Chemical Physics. PCCP

DOI: https://doi.org/10.1039/c8cp07613h · OSTI ID:1975810

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University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

We present a thorough analysis of symmetry breaking observed in Hartree–Fock (HF) solutions of the C₆₀, C₃₆, and C₂₀ fullerenes in order to characterize the nature of electron correlation in them. Our analysis is based on (1) the critical regularization strength to restore symmetry breaking in the recently developed regularized orbital optimized second-order Møller–Plesset perturbation theory (κ-OOMP2), (2) singlet–triplet gaps from various MP2 methods, and (3) natural orbital occupation numbers from restricted coupled-cluster with singles and doubles (RCCSD) and coupled-cluster valence bond with singles and doubles (CCVB-SD). Based on these three independent probes, we conclude that C₃₆ (D6h) exhibits genuine strong correlation and symmetry breaking whereas C₆₀ exhibits artificial HF symmetry breaking and is not strongly correlated. Investigating the critical regularization strength, we discuss strong correlation in C₂₀ at the Jahn–Teller distorted geometries (C_2h, D_2h, C_i, and D_3h) and the Ih geometry. Only C₂₀ (I_h) was found to be strongly correlated while others exhibit artificial HF symmetry breaking. This analysis highlights a useful feature of the recommended κ-OOMP2 method. It is an electronic structure method that describes dynamic correlation, and attenuates strong correlation in MP2 towards zero by regularization. Therefore, κ-OOMP2 will exhibit symmetry breaking in its reference determinant only when correlation is strong (i.e., essential symmetry breaking). Furthermore, artificial symmetry breaking (arising in HF due to neglect of dynamic correlation) thus appears to be removed in κ-OOMP2.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1975810

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 9 Vol. 21; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Distinguishing artificial and essential symmetry breaking in a single determinant: approach and application to the C₆₀, C₃₆, and C₂₀ fullerenes