Toward a Unified Analytical Description of Internal Conversion and Intersystem Crossing in the Photodissociation of Thioformaldehyde. I. Diabatic Singlet States

The photodissociation of thioformaldehyde is an archetypal system for the study of competition between internal conversion and intersystem crossing, which involves its two singlet states (S-0 and S-1) and two triplet states (T-1 and T-2). In order to perform accurate dynamic simulations, either quantum or quasi-classical, it is essential to construct an analytical representation for all necessary electronic structure data. In this work, a diabatic potential energy matrix (DPEM), H-d , for the two singlet states (S-0 and S-1) is reported. The analytical form of DPEM is symmetrized and constructed to reproduce adiabatic energies, energy gradients, and derivative couplings obtained from high-level multireference configuration interaction wave functions. The H-d is fully saturated in the molecular configuration space with a trajectory-guided point sampling approach. This H-d can provide the accurate description of the photodissociation of thioformaldehyde on its singlet states and is also a necessary part for incorporating the spin-orbit couplings into a unified diabatic framework. Preliminary quasi-classical trajectory simulations show that a roaming mechanism also exists in the molecular dissociation channel of thioformaldehyde.

Automated summary

The article reports the diabatic potential energy matrix (DPEM) for the two singlet states (S-0 and S-1) of thioformaldehyde, which is constructed based on high-level multireference configuration interaction wave functions. The saturated H-d in the molecular configuration space provides an accurate description of the photodissociation of thioformaldehyde on its singlet states and is essential for incorporating spin-orbit couplings into a unified framework.