Tracing long-lived atomic coherences generated via molecular conical intersections
Fuente:
arXiv
Guardado en:
| Autores principales: | , , , , , , , , , |
|---|---|
| Formato: | Preprint |
| Publicado: |
2025
|
| Materias: | |
| Acceso en línea: | |
| Etiquetas: |
Agregar Etiqueta
Sin Etiquetas, Sea el primero en etiquetar este registro!
|
| _version_ | 1866910911698042880 |
|---|---|
| author | Rupprecht, Patrick Montorsi, Francesco Xu, Lei Puskar, Nicolette G. Garavelli, Marco Mukamel, Shaul Govind, Niranjan Neumark, Daniel M. Keefer, Daniel Leone, Stephen R. |
| author_facet | Rupprecht, Patrick Montorsi, Francesco Xu, Lei Puskar, Nicolette G. Garavelli, Marco Mukamel, Shaul Govind, Niranjan Neumark, Daniel M. Keefer, Daniel Leone, Stephen R. |
| contents | Accessing coherences is key to fully understand and control ultrafast dynamics of complex quantum systems like molecules. Most photochemical processes are mediated by conical intersections (CIs), which generate coherences between electronic states in molecules. We show with accurate calculations performed on gas-phase methyl iodide that CI-induced electronic coherences of spin-orbit-split states persist in atomic iodine after dissociation. Our simulation predicts a maximum magnitude of vibronic coherence in the molecular regime of 0.75% of the initially photoexcited state population. Upon dissociation, one third of this coherence magnitude is transferred to a long-lived atomic coherence where vibrational decoherence can no longer occur. To trace these dynamics, we propose a table-top experimental approach--heterodyned attosecond four-wave-mixing spectroscopy (Hd-FWM). This technique can temporally resolve small electronic coherence magnitudes and reconstruct the full complex coherence function via phase cycling. Hence, Hd-FWM leads the way to a complete understanding and optimal control of spin-orbit-coupled electronic states in photochemistry. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2504_10674 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | Tracing long-lived atomic coherences generated via molecular conical intersections Rupprecht, Patrick Montorsi, Francesco Xu, Lei Puskar, Nicolette G. Garavelli, Marco Mukamel, Shaul Govind, Niranjan Neumark, Daniel M. Keefer, Daniel Leone, Stephen R. Chemical Physics Accessing coherences is key to fully understand and control ultrafast dynamics of complex quantum systems like molecules. Most photochemical processes are mediated by conical intersections (CIs), which generate coherences between electronic states in molecules. We show with accurate calculations performed on gas-phase methyl iodide that CI-induced electronic coherences of spin-orbit-split states persist in atomic iodine after dissociation. Our simulation predicts a maximum magnitude of vibronic coherence in the molecular regime of 0.75% of the initially photoexcited state population. Upon dissociation, one third of this coherence magnitude is transferred to a long-lived atomic coherence where vibrational decoherence can no longer occur. To trace these dynamics, we propose a table-top experimental approach--heterodyned attosecond four-wave-mixing spectroscopy (Hd-FWM). This technique can temporally resolve small electronic coherence magnitudes and reconstruct the full complex coherence function via phase cycling. Hence, Hd-FWM leads the way to a complete understanding and optimal control of spin-orbit-coupled electronic states in photochemistry. |
| title | Tracing long-lived atomic coherences generated via molecular conical intersections |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2504.10674 |