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

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Trajectory on-the-fly molecular dynamics approach to tunneling splitting in the electronic excited state: A case of tropolone
Journal of Computational Chemistry ( IF 3.4 ) Pub Date : 2020-04-02 , DOI: 10.1002/jcc.26199
Yusuke Ootani ₁ , Aya Satoh ₂ , Yu Harabuchi ₂ , Tetsuya Taketsugu _{2,

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Affiliation

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.

中文翻译：

电子激发态隧道分裂的动态分子动力学方法：以托酚酮为例

在动态分子动力学（TOF-MD）方法的框架中，半经典隧穿方法首次用于评估由于电子激发态分子内质子转移引起的托酚酮的隧穿分裂。为了防止正常振动模式之间的非物理零点振动能量转移，量子零点振动能量仅分配给与分子内质子转移相关的振动模式，而其余模式被视为浴模式。介绍了确定隧道起始点和隧道路径的实用方法。结果表明，随着浴模式能量的增加，隧穿分裂减少。

更新日期：2020-04-02

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