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arXiv · 2402.10195

Using a multistate Mapping Approach to Surface Hopping to predict the Ultrafast Electron Diffraction signal of gas-phase cyclobutanone

Lewis Hutton·Andres Moreno Carrascosa·Andrew W. Prentice·Mats Simmermacher·Johan E. Runeson·Martin J. Paterson·Adam Kirrander
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Abstract

Using the recently developed multistate mapping approach to surface hopping (multistate MASH) method combined with SA(3)-CASSCF(12,12)/aug-cc-pVDZ electronic structure calculations, the gas-phase isotropic ultrafast electron diffraction (UED) of cyclobutanone is predicted and analyzed. After excitation into the n-3s Rydberg state (S$_2$), cyclobutanone can relax through two S$_2$/S$_1$ conical intersections, one characterized by compression of the \ce{CO} bond, the other by dissociation of the $\mathrmα$-CC bond. Subsequent transfer into the ground state (S$_0$) is then achieved via two additional S$_1$/S$_0$ conical intersections that lead to three reaction pathways: $\mathrmα$ ring-opening, ethene/ketene production, and \ce{CO} liberation. The isotropic gas-phase UED signal is predicted from the multistate MASH simulations, allowing for a direct comparison to experimental data. This work, which is a contribution to the cyclobutanone prediction challenge, facilitates the identification of the main photoproducts in the UED signal and thereby emphasizes the importance of dynamics simulations for the interpretation of ultrafast experiments.

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Lewis Hutton, Andres Moreno Carrascosa, Andrew W. Prentice, Mats Simmermacher, Johan E. Runeson, Martin J. Paterson, Adam Kirrander. 2024-02-15. Using a multistate Mapping Approach to Surface Hopping to predict the Ultrafast Electron Diffraction signal of gas-phase cyclobutanone. https://doi.org/10.1063/5.0203667

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