Unraveling Photodimerization of Cyclohexasilane from Molecular Dynamics Studies

Photoinduced reactions of a pair of cyclohexasilane (CHS) monomers are explored by time-dependent excited-state molecular dynamics (TDESMD) calculations. In TDESMD trajectories, one observes vivid reaction events including dimerization and fragmentation. A general reaction pathway is identified as (i) ring-opening formation of a dimer, (ii) rearrangement induced by bond breaking, and (iii) decomposition through the elimination of small fragments. The identified pathway supports the chemistry proposed for the fabrication of silicon-based materials using CHS as a precursor. In addition, we find dimers have smaller HOMO–LUMO gaps and exhibit a red shift and line-width broadening in the computed photoluminescence spectra compared with a pair of CHS monomers.