Excited States of Metal-Adsorbed Dimethyl Disulfide: A TDDFT Study with Cluster Model

[Image: see text] The optical near field refers to a localized light field near a surface that can induce photochemical phenomena such as dipole-forbidden transitions. Recently, the photodissociation of the S–S bond of dimethyl disulfide (DMDS) was investigated using a scanning tunneling microscope with far- and near-field light. This reaction is thought to be initiated by the lowest-energy highest occupied molecular orbital (HOMO) to lowest unoccupied molecular orbital (LUMO) transition of the DMDS molecule under far-field light. In near-field light, photodissociation proceeds at lower photon energies than in far-field light. To gain insight into the underlying mechanism, we theoretically investigated the excited states of DMDS adsorbed on Cu and Ag surfaces modeled by a tetrahedral 20-atom cluster. The frontier orbitals of the molecule were delocalized by the interaction with the metal, resulting in narrowing of the HOMO–LUMO gap energy. The excited-state distribution was analyzed using the Mulliken population analysis, decomposing molecular orbitals into metal and DMDS fragments. The excited states of the intra-DMDS transitions were found over a wider energy range, but at low energies, their oscillator strengths were negligible, which is consistent with the experimental results. Sparse modeling analysis showed that typical electronic transitions differed between the higher and lower excited states. If these low-lying excited states are efficiently excited by near-field light with different selection rules, the S–S bond dissociation reaction can proceed.