Pairwise spin-contamination correction method and DFT study of MnH and H2 dissociation curves

Satyender Goel*, Artëm E. Masunov

*Corresponding author for this work

Research output: Chapter in Book/Report/Conference proceedingConference contribution

6 Scopus citations

Abstract

A clear advantage of broken symmetry (BS) unrestricted density functional theory DFT is qualitatively correct description of bond dissociation process, but its disadvantage is that spin-polarized Slater determinant is no longer a pure spin state (a.k.a. spin contamination). We propose a new approach to eliminate the spin-contamination, based on canonical Natural Orbitals (NO). We derive an expression to extract the energy of the pure singlet state given in terms of energy of BS DFT solution, the occupation number of the bonding NO, and the energy of the higher state built on these bonding and antibonding NOs (as opposed to self-consistent Kohn-Sham orbitals). Thus, unlike spin-contamination correction schemes by Noodleman and Yamaguchi, spin-correction is introduced for each correlated electron pair individually and thus expected to give more accurate results. We validate this approach on two examples, a simple diatomic H2 and transition metal hydride MnH.

Original languageEnglish (US)
Title of host publicationComputational Science - ICCS 2009 - 9th International Conference, Proceedings
Pages141-150
Number of pages10
EditionPART 2
DOIs
StatePublished - 2009
Event9th International Conference on Computational Science, ICCS 2009 - Baton Rouge, LA, United States
Duration: May 25 2009May 27 2009

Publication series

NameLecture Notes in Computer Science (including subseries Lecture Notes in Artificial Intelligence and Lecture Notes in Bioinformatics)
NumberPART 2
Volume5545 LNCS
ISSN (Print)0302-9743
ISSN (Electronic)1611-3349

Other

Other9th International Conference on Computational Science, ICCS 2009
CountryUnited States
CityBaton Rouge, LA
Period5/25/095/27/09

ASJC Scopus subject areas

  • Theoretical Computer Science
  • Computer Science(all)

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