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 journalArticlepeer-review

1 Citation (Scopus)

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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