Communication: An inexpensive, variational, almost black-box, almost size-consistent correction to configuration interaction singles for valence excited states

Xinle Liu, Qi Ou, Ethan Alguire, Joseph E. Subotnik

Research output: Contribution to journalArticlepeer-review

17 Scopus citations

Abstract

Configuration interaction singles (CIS) describe excited electronic states only qualitatively and improvements are imperative as a means of recovering chemical accuracy. In particular, variational improvements would be ideal to account for state crossings and electronic relaxation. To accomplish such an objective, in this communication we present a new suite of algorithms, abbreviated VOO-CIS for variationally orbital optimized CIS. We show below that VOO-CIS yields a uniform improvement to CIS, rebalancing the energies of CT states versus non-CT states within the same framework. Furthermore, VOO-CIS finds energetic corrections for CT states that are even larger than those predicted by CIS(D). The computational cost of VOO-CIS depends strongly on the number of excited states requested (n), but otherwise should be proportional to the cost of CIS itself.

Original languageEnglish (US)
Article number221105
JournalJournal of Chemical Physics
Volume138
Issue number22
DOIs
StatePublished - Jun 14 2013
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • General Physics and Astronomy
  • Physical and Theoretical Chemistry

Fingerprint

Dive into the research topics of 'Communication: An inexpensive, variational, almost black-box, almost size-consistent correction to configuration interaction singles for valence excited states'. Together they form a unique fingerprint.

Cite this