Excited state electronic structure of dimethyl disulfide involved in photodissociation at ∼200 nm.

Dimethyl disulfide (DMDS), one of the smallest organic molecules with an S-S bond, serves as a model system for understanding photofragmentation in polypeptides and proteins. Prior studies of DMDS photodissociation excited at ∼266 nm and ∼248 nm have elucidated the mechanisms of S-S and C-S bond cleavage, which involve the lowest excited electronic states S and S. Far less is known about the dissociation mechanisms and electronic structure of relevant excited states of DMDS excited at ∼200 nm. Herein we present calculations of the electronic structure and properties of electronic states S-S accessed when DMDS is excited at ∼200 nm. Our analysis includes a comparison of theoretical and experimental UV spectra, as well as theoretically predicted one-dimensional cuts through the singlet and triplet potential energy surfaces along the S-S and C-S bond dissociation coordinates. Finally, we present calculations of spin-orbit coupling constants at the Franck-Condon geometry to assess the likelihood of ultrafast intersystem crossing. We show that choosing an accurate yet computationally efficient electronic structure method for calculating the S-S potential energy surfaces along relevant dissociation coordinates is challenging due to excited states with doubly excited character and/or mixed Rydberg-valence character. Our findings demonstrate that the extended multi-state complete active space second-order perturbation theory (XMS-CASPT2) balances this computational efficiency and accuracy, as it captures both the Rydberg character of states in the Franck-Condon region and multiconfigurational character toward the bond-dissociation limits. We compare the performance of XMS-CASPT2 to a new variant of equation of motion coupled cluster theory with single, double, and perturbative triple corrections, EOM-CCSD(T)(a), finding that EOM-CCSD(T)(a) significantly improves the treatment of doubly excited states compared to EOM-CCSD, but struggles to quantitatively capture asymptotic energies along bond dissociation coordinates for these states.