Trajectory on‐the‐fly molecular dynamics approach to tunneling splitting in the electronic excited state: A case of tropolone. Issue 16 (2nd April 2020)

• Record Type: Journal Article
• Authors: Ootani, Yusuke; Satoh, Aya; Harabuchi, Yu; Taketsugu, Tetsuya
• Is Part Of: Journal of computational chemistry. Volume 41:Issue 16(2020)
• Page Start: 1549
• Page End: 1556
• Publication Date: 2020-04-02
• Subjects: excited‐state intramolecular proton transfer -- on‐the‐fly MD -- semiclassical -- tunneling pathway -- tunneling splitting; Chemistry -- Data processing -- Periodicals; 542.85
• DOI: 10.1002/jcc.26199
• Languages: English
• ISSNs: 0192-8651

Abstract

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. Abstract : The semiclassical tunneling method is applied to the evaluation of the tunneling splitting of tropolone in the electronic excited state in a framework of the trajectory on‐the‐fly molecular dynamics approach. Practical ways to determine the tunneling path are introduced. The experimental tunneling splitting value is well reproduced by the present method.