超越Kasha规则的光物理与超越Condon近似的振动光谱的半经典方法。以Azulene为例
Semiclassical Approach to Photophysics Beyond Kasha's Rule and Vibronic Spectroscopy Beyond the Condon Approximation. The Case of Azulene
AI总结：
针对Azulene违反Kasha规则且超出Condon近似的异常光物理现象，本文提出一种结合核半经典动力学与ab initio电子结构的计算方法，并引入新半经典光谱模拟技术，计算结果与实验高度吻合，揭示了非谐性等效应的重要性。
摘要：
Azulene是一个典型的分子，具有来自第二电子激发态的异常荧光，因此违反了Kasha规则，且其发射光谱无法在Condon近似下被理解。为了更好地理解Azulene及其他非传统分子的光物理和光谱学，我们开发了一种系统、通用且高效的计算方法，将核的半经典动力学与ab initio电子结构相结合。首先，为了分析非绝热效应，我们用多重表面退相干表示估算的严格绝热性度量补充了标准布居动力学。其次，我们提出了一种模拟非Condon光谱的新半经典方法，该方法将扩展的解冻高斯近似与高效的单Hessian方法相结合。在一组新实验中记录的Azulene的S$_{1} \leftarrow$ S$_0$和S$_{2} \leftarrow$ S$_0$吸收及S$_{2} \rightarrow$ S$_0$发射光谱与我们的计算非常吻合。我们发现，所评估光谱的准确性需要处理非谐性、Herzberg--Teller和模式混合效应。
英文摘要：
Azulene is a prototypical molecule with an anomalous fluorescence from the second excited electronic state, thus violating Kasha's rule, and with an emission spectrum that cannot be understood within the Condon approximation. To better understand photophysics and spectroscopy of azulene and other non-conventional molecules, we develop a systematic, general, and efficient computational approach combining semiclassical dynamics of nuclei with ab initio electronic structure. First, to analyze the nonadiabatic effects, we complement the standard population dynamics by a rigorous measure of adiabaticity, estimated with the multiple-surface dephasing representation. Second, we propose a new semiclassical method for simulating non-Condon spectra, which combines the extended thawed Gaussian approximation with the efficient single-Hessian approach. S$_{1} \leftarrow$ S$_0$ and S$_{2} \leftarrow$ S$_0$ absorption and S$_{2} \rightarrow$ S$_0$ emission spectra of azulene, recorded in a new set of experiments, agree very well with our calculations. We find that accuracy of the evaluated spectra requires the treatment of anharmonicity, Herzberg--Teller, and mode-mixing effects.
机构、总结、中文摘要均由AI分析而来，可能存在错误，请以论文正文为准。
