Quantum Dynamics Predicts Coherent Oscillatory Behavior in the Early-times of a Photoisomerization Reaction
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arXiv
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| Main Authors: | , , , , , , |
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| Format: | Preprint |
| Published: |
2025
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| _version_ | 1866912418685255680 |
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| author | Aarabi, Mohammad Marsili, Emanuele Olivucci, Massimo Lauvergnat, David Agostini, Federica Garavelli, Marco Santoro, Fabrizio |
| author_facet | Aarabi, Mohammad Marsili, Emanuele Olivucci, Massimo Lauvergnat, David Agostini, Federica Garavelli, Marco Santoro, Fabrizio |
| contents | In this work, we study the quantum dynamics of a photoisomerization reaction employing a two-electronic-state three-vibrational-mode model of the 2-cis-penta-2,4-dieniminium cation (cis-PSB3). In particular, we address two main issues: the challenges encountered in properly converging quantum dynamics calculations, even when a reduced-dimensionality molecular model is used; the emergence of a coherent oscillatory behavior in the formation of the trans isomer upon photoexcitation of cis-PSB3. The two issues are strictly related, since only upon reliable convergence, the simulated dynamics is able to capture the large amplitude motion associated to the torsion around the reactive bond, typical of photoisomerizations, which is due to the large amount of kinetic energy acquired by the vibrational modes after light excitation. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2505_20823 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | Quantum Dynamics Predicts Coherent Oscillatory Behavior in the Early-times of a Photoisomerization Reaction Aarabi, Mohammad Marsili, Emanuele Olivucci, Massimo Lauvergnat, David Agostini, Federica Garavelli, Marco Santoro, Fabrizio Chemical Physics In this work, we study the quantum dynamics of a photoisomerization reaction employing a two-electronic-state three-vibrational-mode model of the 2-cis-penta-2,4-dieniminium cation (cis-PSB3). In particular, we address two main issues: the challenges encountered in properly converging quantum dynamics calculations, even when a reduced-dimensionality molecular model is used; the emergence of a coherent oscillatory behavior in the formation of the trans isomer upon photoexcitation of cis-PSB3. The two issues are strictly related, since only upon reliable convergence, the simulated dynamics is able to capture the large amplitude motion associated to the torsion around the reactive bond, typical of photoisomerizations, which is due to the large amount of kinetic energy acquired by the vibrational modes after light excitation. |
| title | Quantum Dynamics Predicts Coherent Oscillatory Behavior in the Early-times of a Photoisomerization Reaction |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2505.20823 |