Locating conical intersections relevant to photochemical reactions

Bernhard Dick, Yehuda Haas, Shmuel Zilberg

Research output: Contribution to journalArticlepeer-review

23 Scopus citations

Abstract

A new computerized method for locating conical intersections of interest in photochemistry is presented. The search is based on the Longuet-Higgins phase change theorem (Berry phase) which provides the subspace required for the initial search. The subspace is approximated as a plane containing three stable structures lying on a Longuet-Higgins loop. The search is conducted for a minimum of ΔE, the energy difference between two electronic states. It is started using up to three points within the circle defined by the three structures; symmetry, if relevant, is helpful but not essential. Since a two-dimensional subspace of the large 3N - 6 space is used, the search that uses either Cartesian or internal coordinates is efficient and yields a degeneracy after a few iterations. Given that not all degrees of freedom are included in the search, usually a high lying part of the conical intersection is initially located. The system is subsequently optimized along all coordinates keeping ΔE as close to zero as desired. The method is demonstrated for the symmetric H3 system and also for the butadiene-cyclobutene-bicyclobutane system in which the three stable structures are not equivalent. The method is general and can be extended to any photochemical system.

Original languageEnglish
Pages (from-to)65-77
Number of pages13
JournalChemical Physics
Volume347
Issue number1-3
DOIs
StatePublished - 23 May 2008
Externally publishedYes

Keywords

  • Bicyclobutane
  • Butadiene
  • Conical intersections
  • Cyclobutene
  • Longuet-Higgins loop

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