Simulation of Pump-Push Molecular Dynamics in the Heptazine-H2O Complex
Fuente:
arXiv
Gespeichert in:
| Hauptverfasser: | , , , |
|---|---|
| Format: | Preprint |
| Veröffentlicht: |
2025
|
| Schlagworte: | |
| Online-Zugang: | |
| Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
| _version_ | 1866918011356577792 |
|---|---|
| author | Pios, Sebastian V. Gelin, Maxim F. Domcke, Wolfgang Chen, Lipeng |
| author_facet | Pios, Sebastian V. Gelin, Maxim F. Domcke, Wolfgang Chen, Lipeng |
| contents | Pump-push-probe spectroscopy was employed for the exploration of charge-separation processes in organic photovoltaic blends as well as for proton-coupled electron-transfer (PCET) reactions in hydrogen-bonded complexes of tri-anisole-heptazine with substituted phenols in organic solvents. In the present work, the electron and proton transfer dynamics driven by a femtosecond pump pulse and a time-delayed femtosecond push pulse has been studied with ab initio on-the-fly nonadiabatic trajectory calculations for the hydrogen-bonded heptazine-H2O complex. While the dynamics following the pump pulse is dominated by ultrafast radiationless energy relaxation to the long-lived lowest singlet excited state (S1) of the heptazine chromophore with only minor PCET reactivity, the re-excitation of the transient S1 population by the push pulse results in a much higher PCET reaction probability. These results illustrate that pump-push excitation has the potential to unravel the individual electron and proton transfer processes of PCET reactions on femtosecond time scales. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2505_03355 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | Simulation of Pump-Push Molecular Dynamics in the Heptazine-H2O Complex Pios, Sebastian V. Gelin, Maxim F. Domcke, Wolfgang Chen, Lipeng Chemical Physics Pump-push-probe spectroscopy was employed for the exploration of charge-separation processes in organic photovoltaic blends as well as for proton-coupled electron-transfer (PCET) reactions in hydrogen-bonded complexes of tri-anisole-heptazine with substituted phenols in organic solvents. In the present work, the electron and proton transfer dynamics driven by a femtosecond pump pulse and a time-delayed femtosecond push pulse has been studied with ab initio on-the-fly nonadiabatic trajectory calculations for the hydrogen-bonded heptazine-H2O complex. While the dynamics following the pump pulse is dominated by ultrafast radiationless energy relaxation to the long-lived lowest singlet excited state (S1) of the heptazine chromophore with only minor PCET reactivity, the re-excitation of the transient S1 population by the push pulse results in a much higher PCET reaction probability. These results illustrate that pump-push excitation has the potential to unravel the individual electron and proton transfer processes of PCET reactions on femtosecond time scales. |
| title | Simulation of Pump-Push Molecular Dynamics in the Heptazine-H2O Complex |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2505.03355 |