期刊
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
卷 12, 期 2, 页码 774-786出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.jctc.5b01017
关键词
-
资金
- European Research Council under European Union/ERC [320951]
- Italian MIUR (FIRB) [RBFR122HFZ]
The temperature dependence of the rate constants in radiative and nonradiative decays from excited electronic states has been studied using a time-dependent correlation function approach in the framework of the adiabatic representation and the harmonic oscillator approximation. The present work analyzes the vibrational aspect of the processes, which gives rise to the temperature dependence, with the inclusion of mode-mixing, as well as of frequency change effects. The temperature dependence of the rate constants shows a contrasting nature, depending on whether the process has been addressed within the Franck-Condon approximation or beyond it. The calculation of the Duschinsky matrix and the shift vector between the normal modes of the two states can be done in Cartesian and/or internal coordinates, depending on the flexibility of the investigated molecule. A new computational code has been developed to calculate the rates of intersystem crossing, internal conversion, and fluorescence for selected molecules as functions of temperature.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据