Ultrafast photochemistry and electron-diffraction spectra in n->(3s) Rydberg excited cyclobutanone resolved at the multireference perturbative level

2024/02/15 by Jaiswal, V. K., Montorsi, F., Aleotti, F. +6
#Chemical Physics (physics.chem-ph) #FOS: Physical sciences

paper · doi:10.48550/arxiv.2402.09873

Abstract

We study the ultrafast time evolution of cyclobutanone excited to singlet n-->Rydberg state through XMS-CASPT2 nonadiabatic surface-hopping simulations. These dynamics predict relaxation to ground-state with a timescale of 822 +/- 45 fs with minimal involvement of triplets. The major relaxation path to the ground-state involves a three-state degeneracy region and leads to variety of fragmented photoproducts. We simulate the resulting time-resolved electron-diffraction spectra which track the relaxation of the excited state and the formation of various photoproducts in the ground-state.

Related

• The Photochemistry of Rydberg Excited Cyclobutanone: Photoinduced Processes and Ground State Dynamics
• Photofragmentation of cyclobutanone at 200 nm: TD-DFT vs CASSCF electron diffraction
• A CASSCF/MRCI Trajectory Surface Hopping Simulation of the Photochemical Dynamics and the Gas Phase Ultrafast Electron Diffraction Patterns of Cyclobutanone
• Imaging the photochemical dynamics of cyclobutanone with MeV ultrafast electron diffraction
• Imaging the Photochemistry of Cyclobutanone using Ultrafast Electron Diffraction: Experimental Results