A surface hopping algorithm for nonadiabatic minimum energy path calculations

Igor Schapiro, Daniel Roca-Sanjuán, Roland Lindh, Massimo Olivucci

Research output: Contribution to journalArticlepeer-review

8 Scopus citations

Abstract

The article introduces a robust algorithm for the computation of minimum energy paths transiting along regions of near-to or degeneracy of adiabatic states. The method facilitates studies of excited state reactivity involving weakly avoided crossings and conical intersections. Based on the analysis of the change in the multiconfigurational wave function the algorithm takes the decision whether the optimization should continue following the same electronic state or switch to a different state. This algorithm helps to overcome convergence difficulties near degeneracies. The implementation in the MOLCAS quantum chemistry package is discussed. To demonstrate the utility of the proposed procedure four examples of application are provided: thymine, asulam, 1,2-dioxetane, and a three-double-bond model of the 11-cis-retinal protonated Schiff base.

Original languageAmerican English
Pages (from-to)312-320
Number of pages9
JournalJournal of Computational Chemistry
Volume36
Issue number5
DOIs
StatePublished - 15 Feb 2015
Externally publishedYes

Bibliographical note

Publisher Copyright:
© 2015 Wiley Periodicals, Inc.

Keywords

  • Asulam
  • CASSCF
  • Dioxetane
  • Minimum energy path
  • Retinal
  • Surface hopping algorithm
  • Thymine

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