Symmetry dependence and universality of practical algebraic functionals in density-matrix-functional theory

Gritsenko, Oleg V., Wang, Jian and Knowles, Peter J. ORCID: https://orcid.org/0000-0003-4657-6331 2019. Symmetry dependence and universality of practical algebraic functionals in density-matrix-functional theory. Physical Review A 99 (4) , -. 10.1103/PhysRevA.99.042516

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Abstract

When dealing with a fully symmetrical ground state, the symmetry dependence of the universal Hohenberg-Kohn energy functional F[γ] of the first-order reduced density matrix (RDM) γ can be conveniently neglected. The situation changes drastically in the case of the dissociation of a symmetrical molecule with the state crossing, in the course of which the potential energy curve of the initial non-fully symmetrical ground state is eventually crossed with that of the fully symmetrical state. In this case, as is demonstrated in the present paper, the second-order RDM Γij,kl in the representation of the natural orbitals (NOs) is symmetry dependent. Since Γij,kl is the goal in the design of Γij,kl(n) as a functional of NO occupations {n}, which is part of a practical density matrix functional F[γ],Γij,kl(n) must also depend on the symmetry, especially the irreducible representation of the symmetry group. The result has immediate implications for study of structural (or phase) transitions based on a single symmetry-independent functional. The demonstration is given in the minimal-base model of the dissociation of the prototype H4 molecule in the rhombic structure.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Chemistry Advanced Research Computing @ Cardiff (ARCCA)
Publisher:	American Physical Society
ISSN:	2469-9926
Date of First Compliant Deposit:	14 May 2019
Date of Acceptance:	24 April 2019
Last Modified:	02 May 2023 20:07
URI:	https://orca.cardiff.ac.uk/id/eprint/122430

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