Journal
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
Volume 19, Issue 18, Pages 6414-6424Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jctc.3c00628
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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.
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.
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