Communication: Extended multi-state complete active space second-order perturbation theory: Energy and nuclear gradients

Toru Shiozaki*, Werner Gyroffy, Paolo Celani, Hans Joachim Werner

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

210 Scopus citations

Abstract

The extended multireference quasi-degenerate perturbation theory, proposed by Granovsky [J. Chem. Phys. 134, 214113 (2011)], is combined with internally contracted multi-state complete active space second-order perturbation theory (XMS-CASPT2). The first-order wavefunction is expanded in terms of the union of internally contracted basis functions generated from all the reference functions, which guarantees invariance of the theory with respect to unitary rotations of the reference functions. The method yields improved potentials in the vicinity of avoided crossings and conical intersections. The theory for computing nuclear energy gradients for MS-CASPT2 and XMS-CASPT2 is also presented and the first implementation of these gradient methods is reported. A number of illustrative applications of the new methods are presented.

Original languageEnglish (US)
Article number081106
JournalJournal of Chemical Physics
Volume135
Issue number8
DOIs
StatePublished - Aug 28 2011

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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