Saved in:
| Main Authors: | , , , , , , , , , |
|---|---|
| Format: | Preprint |
| Published: |
2020
|
| Subjects: | |
| Online Access: | https://arxiv.org/abs/2001.08414 |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| _version_ | 1866912043969282048 |
|---|---|
| author | Prlj, Antonio Begušić, Tomislav Zhang, Zhan Tong Fish, George Cameron Wehrle, Marius Zimmermann, Tomáš Choi, Seonghoon Roulet, Julien Moser, Jacques-Edouard Vaníček, Jiří |
| author_facet | Prlj, Antonio Begušić, Tomislav Zhang, Zhan Tong Fish, George Cameron Wehrle, Marius Zimmermann, Tomáš Choi, Seonghoon Roulet, Julien Moser, Jacques-Edouard Vaníček, Jiří |
| contents | 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. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2001_08414 |
| institution | arXiv |
| publishDate | 2020 |
| record_format | arxiv |
| spellingShingle | Semiclassical Approach to Photophysics Beyond Kasha's Rule and Vibronic Spectroscopy Beyond the Condon Approximation. The Case of Azulene Prlj, Antonio Begušić, Tomislav Zhang, Zhan Tong Fish, George Cameron Wehrle, Marius Zimmermann, Tomáš Choi, Seonghoon Roulet, Julien Moser, Jacques-Edouard Vaníček, Jiří Chemical Physics Computational Physics Quantum Physics 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. |
| title | Semiclassical Approach to Photophysics Beyond Kasha's Rule and Vibronic Spectroscopy Beyond the Condon Approximation. The Case of Azulene |
| topic | Chemical Physics Computational Physics Quantum Physics |
| url | https://arxiv.org/abs/2001.08414 |