Toward a Resolution of the Static Correlation Problem in Density Functional Theory from Semidefinite Programming

Daniel Gibney, Jan Niklas Boyn, David A. Mazziotti

Research output: Contribution to journalArticlepeer-review

16 Scopus citations

Abstract

Kohn-Sham density functional theory (DFT) has long struggled with the accurate description of strongly correlated and open shell systems, and improvements have been minor even in the newest hybrid functionals. In this Letter we treat the static correlation in DFT when frontier orbitals are degenerate by the means of using a semidefinite programming (SDP) approach to minimize the system energy as a function of the N-representable, non-idempotent 1-electron reduced density matrix. While showing greatly improved singlet-triplet gaps for local density approximation and generalized gradient approximation (GGA) functionals, the SDP procedure reveals flaws in modern meta and hybrid GGA functionals, which show no major improvements when provided with an accurate electron density.

Original languageEnglish (US)
Pages (from-to)385-391
Number of pages7
JournalJournal of Physical Chemistry Letters
Volume12
Issue number1
DOIs
StatePublished - Jan 14 2021
Externally publishedYes

Bibliographical note

Publisher Copyright:
©

Fingerprint

Dive into the research topics of 'Toward a Resolution of the Static Correlation Problem in Density Functional Theory from Semidefinite Programming'. Together they form a unique fingerprint.

Cite this