Ultrafast photoinduced dynamics in 1,3-cyclohexadiene: a comparison of trajectory surface hopping schemes
Photoinduced nonadiabatic processes play a crucial role in a wide range of disciplines, from fundamental steps in biology to modern applications in advanced materials science. A theoretical understanding of these processes is highly desirable, and trajectory surface hopping (TSH) has proven to be a...
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| Main Authors: | , , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
July 1, 2024
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| In: |
Journal of chemical theory and computation
Year: 2024, Volume: 20, Issue: 14, Pages: 5796-5806 |
| ISSN: | 1549-9626 |
| DOI: | 10.1021/acs.jctc.4c00012 |
| Online Access: | Verlag, kostenfrei, Volltext: https://doi.org/10.1021/acs.jctc.4c00012
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| Author Notes: | Edison X. Salazar, Maximilian F.S.J. Menger, and Shirin Faraji |
| Summary: | Photoinduced nonadiabatic processes play a crucial role in a wide range of disciplines, from fundamental steps in biology to modern applications in advanced materials science. A theoretical understanding of these processes is highly desirable, and trajectory surface hopping (TSH) has proven to be a well-suited framework for a wide range of systems. In this work, we present a comprehensive comparison between two TSH algorithms, the conventional Tully’s fewest switches surface hopping (FSSH) scheme and the Landau-Zener surface hopping (LZSH), to study the photoinduced ring-opening of 1,3-cyclohexadiene (CHD) to 1,3,5-hexatriene at the spin-flip time-dependent density functional theory (SF-TDDFT) level of theory. Additionally, we compare our results with a literature study at the extended multistate complete active space second-order perturbation theory method (XMS-CASPT2) level of theory. Our results show that the average population and lifetimes estimated with LZSH using SF-TDDFT are closer to the literature (using multireference methods) than those estimated with FSSH using SF-TDDFT. The latter speaks in favor of applying LZSH in combination with the SF-TDDFT method to study larger and more complex systems such as molecular photoswitches where the CHD molecule acts as a backbone. In addition, we present an implementation of Tully’s FSSH algorithm as an extension to the PySurf software package. |
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| Item Description: | Gesehen am 08.01.2025 |
| Physical Description: | Online Resource |
| ISSN: | 1549-9626 |
| DOI: | 10.1021/acs.jctc.4c00012 |