A Vibronic Coupling Model to Study the Nonadiabatic Dynamics of Polyenes
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| Main Authors: | , , , |
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| Format: | Preprint |
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2025
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| _version_ | 1866912914661703680 |
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| author | Georges, Timothy N. Summerley, Louis Runeson, Johan E. Barford, William |
| author_facet | Georges, Timothy N. Summerley, Louis Runeson, Johan E. Barford, William |
| contents | We develop a linear vibronic coupling (LVC) model for polyenes described by the extended Hubbard-Peierls Hamiltonian. This model is applied to trans-hexatriene to benchmark quantum-classical dynamics methods against fully quantum simulations. We find that surface-hopping methods describe short times more accurately than multi-trajectory Ehrenfest. None of the quantum-classical methods studied obtain the long-time population oscillations found in fully quantum simulations. Varying the parameters of the LVC Hamiltonian, we find that surface hopping reproduces the correct trends in the long-time dynamics across a wide range of parameters, but generally overestimates the degree of internal conversion. On the other hand, multi-trajectory Ehrenfest gives more accurate long-time populations in proximity to the hexatriene parameter set. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2511_20433 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | A Vibronic Coupling Model to Study the Nonadiabatic Dynamics of Polyenes Georges, Timothy N. Summerley, Louis Runeson, Johan E. Barford, William Chemical Physics We develop a linear vibronic coupling (LVC) model for polyenes described by the extended Hubbard-Peierls Hamiltonian. This model is applied to trans-hexatriene to benchmark quantum-classical dynamics methods against fully quantum simulations. We find that surface-hopping methods describe short times more accurately than multi-trajectory Ehrenfest. None of the quantum-classical methods studied obtain the long-time population oscillations found in fully quantum simulations. Varying the parameters of the LVC Hamiltonian, we find that surface hopping reproduces the correct trends in the long-time dynamics across a wide range of parameters, but generally overestimates the degree of internal conversion. On the other hand, multi-trajectory Ehrenfest gives more accurate long-time populations in proximity to the hexatriene parameter set. |
| title | A Vibronic Coupling Model to Study the Nonadiabatic Dynamics of Polyenes |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2511.20433 |