A coupled-trajectory approach for decoherence, frustrated hops and internal consistency in surface hopping
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arXiv
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| Autori principali: | , , , , |
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| Natura: | Preprint |
| Pubblicazione: |
2024
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| _version_ | 1866911128711331840 |
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| author | Ibele, Lea M. Gil, Eduarda Sangiogo Schürger, Peter Noc, Rodrigue Agostini, Federica |
| author_facet | Ibele, Lea M. Gil, Eduarda Sangiogo Schürger, Peter Noc, Rodrigue Agostini, Federica |
| contents | We address the issues of decoherence, frustrated hops and internal consistency in surface hopping. We demonstrate that moving away from an independent-trajectory picture is the strategy which allows us to propose a robust surface hopping scheme overcoming all these issues at once. Based on the exact factorization and on the idea of coupled trajectories, we consider the swarm of trajectories, that mimics the nuclear dynamics in nonadiabatic processes, as a unique entity. In this way, imposing energy conservation of the swarm and allowing the trajectories to share energy when hops occur clearly indicates the route towards a new surface hopping scheme. Encouraging results are reported, in terms of electronic and vibrational time-dependent properties on the photodynamics of fulvene and 4-(dimethyloamino)benzonitrile, modeled with a full-dimensional linear vibronic coupling Hamiltonian. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2412_04958 |
| institution | arXiv |
| publishDate | 2024 |
| record_format | arxiv |
| spellingShingle | A coupled-trajectory approach for decoherence, frustrated hops and internal consistency in surface hopping Ibele, Lea M. Gil, Eduarda Sangiogo Schürger, Peter Noc, Rodrigue Agostini, Federica Chemical Physics We address the issues of decoherence, frustrated hops and internal consistency in surface hopping. We demonstrate that moving away from an independent-trajectory picture is the strategy which allows us to propose a robust surface hopping scheme overcoming all these issues at once. Based on the exact factorization and on the idea of coupled trajectories, we consider the swarm of trajectories, that mimics the nuclear dynamics in nonadiabatic processes, as a unique entity. In this way, imposing energy conservation of the swarm and allowing the trajectories to share energy when hops occur clearly indicates the route towards a new surface hopping scheme. Encouraging results are reported, in terms of electronic and vibrational time-dependent properties on the photodynamics of fulvene and 4-(dimethyloamino)benzonitrile, modeled with a full-dimensional linear vibronic coupling Hamiltonian. |
| title | A coupled-trajectory approach for decoherence, frustrated hops and internal consistency in surface hopping |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2412.04958 |