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

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 $\alpha$-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: $\alpha$ 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.

Cyclobutanone prediction challenge in Journal of Chemical Physics

References in corpus (10)

• On-the-fly CASPT2 surface hopping dynamics
• Generalized spin mapping for quantum-classical dynamics
• A mapping approach to surface hopping
• A multi-state mapping approach to surface hopping
• Which Electronic Structure Method to Choose in Trajectory Surface Hopping Dynamics Simulations? Azomethane as a Case Study
• Excited Electronic States in Total Isotropic Scattering From Molecules
• Exciton dynamics from the mapping approach to surface hopping: Comparison with Förster and Redfield theories
• Ab-Initio Surface Hopping and Multiphoton Ionisation Study of the Photodissociation Dynamics of CS${}_2$
• Reference Vertical Excitation Energies for Transition Metal Compounds
• Robust inversion of time-resolved data via forward-optimisation in a trajectory basis

Cited by in corpus (2)

• Imaging the photochemical dynamics of cyclobutanone with MeV ultrafast electron diffraction
• Electronic structure of norbornadiene and quadricyclane