Photoisomerization of silyl-substituted cyclobutadiene induced by σ → π* excitation: a computational study

Photoinduced chemical processes upon Franck-Condon (FC) excitation in tetrakis(trimethylsilyl)-cyclobutadiene (TMS-CBD) have been investigated through the exploration of potential energy surface crossings among several low-lying excited states using the complete active space self-consistent field (CASSCF) method. Vertical excitation energies are also computed with the equation-of-motion coupled-cluster model with single and double excitations (EOM-CCSD) as well as the multireference Møller-Plesset (MRMP) methods. Upon finding an excellent coincidence between the computational results and experimental observations, it is suggested that the Franck-Condon excited state does not correspond to the first π-π* single excitation state (S1, 1(1)B1 state in terms of D2 symmetry), but to the second (1)B1 state (S3), which is characterized as a σ-π* single excitation state. Starting from the Franck-Condon region, a series of conical intersections (CIs) are located along one isomerization channel and one dissociation channel. Through the isomerization channel, TMS-CBD is transformed to tetrakis(trimethylsilyl)-tetrahedrane (TMS-THD), and this isomerization process could take place by passing through a "tetra form" conical intersection. On the other hand, the dissociation channel yielding two bis(trimethylsilyl)-acetylene (TMS-Ac) molecules through further stretching of the longer C-C bonds might be more competitive than the isomerization channel after excitation into S3 state. This mechanistic picture is in good agreement with recently reported experimental observations.