دورية
Semiclassical Approach to Photophysics Beyond Kasha’s Rule and Vibronic Spectroscopy Beyond the Condon Approximation. The Case of Azulene
| العنوان: | Semiclassical Approach to Photophysics Beyond Kasha’s Rule and Vibronic Spectroscopy Beyond the Condon Approximation. The Case of Azulene |
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| المؤلفون: | Prlj, Antonio, Begušić, Tomislav, Zhang, Zhan Tong, Fish, George Cameron, Wehrle, Marius, Zimmermann, Tomáš, Choi, Seonghoon, Roulet, Julien, Moser, Jacques-Edouard, Vaníček, Jiří |
| المصدر: | Journal of Chemical Theory and Computation; April 2020, Vol. 16 Issue: 4 p2617-2626, 10p |
| مستخلص: | 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 the photophysics and spectroscopy of azulene and other nonconventional molecules, we developed a systematic, general, and efficient computational approach combining the semiclassical dynamics of nuclei with ab initioelectronic 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. S1← S0and S2← S0absorption and S2→ S0emission 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. |
| قاعدة البيانات: | Supplemental Index |
| تدمد: | 15499618 15499626 |
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| DOI: | 10.1021/acs.jctc.0c00079 |