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Promoting-mode free formalism for excited state radiationless decay process with Duschinsky rotation effect

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Abstract

In the present work, through the path integral of Gaussian type correlation function, a new formalism based on Fermi-Golden Rule for calculating the rate constant of nonradiative decay process with Duschinsky rotation effect in polyatomic molecules is developed. The advantage of the present path-integral formalism is promoting-mode free. In order to get the rate constant, a “transition rate matrix” needs to be calculated. The rate constant calculated previously is only an approximation of diagonal elements of our “transition rate matrix”. The total rate should be the summation over all the matrix elements.

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Authors and Affiliations

  1. Key Laboratory of Organic Solids, Beijing National Laboratory for Molecular Sciences (BNLMS), Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China

    YingLi Niu, Qian Peng & ZhiGang Shuai

  2. Department of Chemistry, Tsinghua University, Beijing, 100084, China

    ZhiGang Shuai

Authors
  1. YingLi Niu
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  2. Qian Peng
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  3. ZhiGang Shuai
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Correspondence to ZhiGang Shuai.

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Supported by the National Natural Science Foundation of China (Grant Nos. 10425420, 20433070 and 90503013)

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Niu, Y., Peng, Q. & Shuai, Z. Promoting-mode free formalism for excited state radiationless decay process with Duschinsky rotation effect. Sci. China Ser. B-Chem. 51, 1153–1158 (2008). https://doi.org/10.1007/s11426-008-0130-4

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  • DOI: https://doi.org/10.1007/s11426-008-0130-4

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