Embedded mean-field theory with block-orthogonalized partitioning

Feizhi Ding, Frederick R. Manby, Thomas F. Miller*

*Corresponding author for this work

Research output: Contribution to journalArticle (Academic Journal)peer-review

23 Citations (Scopus)
324 Downloads (Pure)

Abstract

Embedded mean-field theory (EMFT) provides a simple, flexible framework for describing subsystems at different levels of mean-field theory. Subsystems are defined by partitioning a one-particle basis set, with a natural choice being the atomic orbital (AO) basis. Although generally well behaved, EMFT with AO partitioning can exhibit unphysical collapse of the self-consistent solution. To avoid this issue, we introduce subsystem partitioning of a block-orthogonalized (BO) basis set; this eliminates the unphysical collapse without significantly increasing computational cost. We also investigate a non-self-consistent implementation of EMFT, in which the density matrix is obtained using BO partitioning and the final energy evaluated using AO partitioning; this density-corrected EMFT approach is found to yield more accurate energies than BO partitioning while also avoiding issues of the unphysical collapse. Using these refined implementations of EMFT, previously proposed descriptions of the exact-exchange coupling between subsystems are compared: although the EX1 coupling scheme is slightly more accurate than EX0, the small improvement does not merit its substantially greater computational cost.

Original languageEnglish
Pages (from-to)1605-1615
Number of pages11
JournalJournal of Chemical Theory and Computation
Volume13
Issue number4
Early online date28 Feb 2017
DOIs
Publication statusPublished - 11 Apr 2017

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