Ab Initio Simulation of Femtosecond Time-Resolved Multi-Pulse Spectroscopies applied to the Heptazine$\cdots$H$_2$O Complex
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| Formato: | Preprint |
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2026
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| _version_ | 1866911540825817088 |
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| author | Pios, Sebastian V. Gelin, Maxim F. Domcke, Wolfgang Chen, Lipeng |
| author_facet | Pios, Sebastian V. Gelin, Maxim F. Domcke, Wolfgang Chen, Lipeng |
| contents | In multi-dimensional time-resolved spectroscopic experiments, multiple (more than two) short laser pulses with variable pulse delay times are employed for the time-resolved exploration of the photoinduced dynamics of molecular chromophores. In the present work, the quasi-classical doorway-window (DW) methodology recently developed for transient absorption pump-probe (PP) spectroscopy [M. F. Gelin et al., J. Chem. Theory Comput. 2021, 17, 2394] has been generalized to multi-pulse spectroscopies. Pump-push-probe (PPP) spectroscopy (involving three laser pulses) and pump-induced two-dimensional (P-2D) spectroscopy (involving five laser pulses) are considered as specific examples. The quasi-classical DW approximation results in conceptually simple and computationally efficient simulation protocols which are suitable for implementation with $ab$ $initio$ on-the-fly electronic-structure calculations. Simulations of PPP and P-2D spectra performed for the hydrogen-bonded heptazine$\cdots$H$_2$O complex illustrate that pump-stimulated experiments provide much richer information on the ultrafast radiationless relaxation dynamics of the excited electronic states of the heptazine$\cdots$H$_2$O complex than conventional PP and 2D experiments. |
| format | Preprint |
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arxiv_https___arxiv_org_abs_2603_22671 |
| institution | arXiv |
| publishDate | 2026 |
| record_format | arxiv |
| spellingShingle | Ab Initio Simulation of Femtosecond Time-Resolved Multi-Pulse Spectroscopies applied to the Heptazine$\cdots$H$_2$O Complex Pios, Sebastian V. Gelin, Maxim F. Domcke, Wolfgang Chen, Lipeng Chemical Physics In multi-dimensional time-resolved spectroscopic experiments, multiple (more than two) short laser pulses with variable pulse delay times are employed for the time-resolved exploration of the photoinduced dynamics of molecular chromophores. In the present work, the quasi-classical doorway-window (DW) methodology recently developed for transient absorption pump-probe (PP) spectroscopy [M. F. Gelin et al., J. Chem. Theory Comput. 2021, 17, 2394] has been generalized to multi-pulse spectroscopies. Pump-push-probe (PPP) spectroscopy (involving three laser pulses) and pump-induced two-dimensional (P-2D) spectroscopy (involving five laser pulses) are considered as specific examples. The quasi-classical DW approximation results in conceptually simple and computationally efficient simulation protocols which are suitable for implementation with $ab$ $initio$ on-the-fly electronic-structure calculations. Simulations of PPP and P-2D spectra performed for the hydrogen-bonded heptazine$\cdots$H$_2$O complex illustrate that pump-stimulated experiments provide much richer information on the ultrafast radiationless relaxation dynamics of the excited electronic states of the heptazine$\cdots$H$_2$O complex than conventional PP and 2D experiments. |
| title | Ab Initio Simulation of Femtosecond Time-Resolved Multi-Pulse Spectroscopies applied to the Heptazine$\cdots$H$_2$O Complex |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2603.22671 |