Resolving the Experimental Photoelectron Spectra of CAl3Si

The experimental photoelectron spectra concerning the six electronic states of CAl3Si– are resolved through electronic structure calculations and quantum nuclear dynamics in this study. It incorporates a model diabatic Hamiltonian to evaluate the coupling parameters and fit the potential energy curves (PECs). The analysis of these PECs showed us that there are sufficient nonadiabatic effects in the photoelectron spectra through the presence of various conical intersections. Poisson intensity distributions (PIDs) and the wave packet density plots are utilized for assigning the fundamental and first overtone excitations. The nuclear dynamics study is accomplished by employing time-dependent (TD) and time-independent (TI) quantum chemistry methods. Ultimately, our theoretical results concurred well with the experimental findings exhibiting vibronic coupling amidst the nearly positioned electronic states.