Trajectory on-the-fly molecular dynamics approach to tunneling splitting in the electronic excited state: A case of tropolone

Yusuke Ootani, Aya Satoh, Yu Harabuchi, Tetsuya Taketsugu

Research output: Contribution to journalArticle

Abstract

The semiclassical tunneling method is applied to evaluate the tunneling splitting of tropolone due to the intramolecular proton transfer in the electronic excited state, first time, in a framework of the trajectory on-the-fly molecular dynamics (TOF-MD) approach. To prevent unphysical zero-point vibrational energy transfer among the normal modes of vibration, quantum zero-point vibrational energies are assigned only to the vibrational modes related to intramolecular proton transfer, whereas the remaining modes are treated as bath modes. Practical ways to determine the tunnel-initiating points and tunneling path are introduced. It is shown that the tunneling splitting decreases as the bath-mode energy increases. The experimental tunneling splitting value is well reproduced by the present TOF-MD approach based on the Wentzel-Kramers-Brillouin (WKB) approximation.

Original languageEnglish
Pages (from-to)1549-1556
Number of pages8
JournalJournal of Computational Chemistry
Volume41
Issue number16
DOIs
Publication statusPublished - 2020 Jun 15

Keywords

  • excited-state intramolecular proton transfer
  • on-the-fly MD
  • semiclassical
  • tunneling pathway
  • tunneling splitting

ASJC Scopus subject areas

  • Chemistry(all)
  • Computational Mathematics

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