Identifying and tracing potential energy surfaces of electronic excitations with specific character via their transition origins: application to oxirane.

摘要: We show that the transition origins of electronic excitations identified by quantified natural orbital (QNTO) analysis can be employed to connect potential energy surfaces (PESs) according their character across a wide range molecular geometries. This is achieved locating switching adiabatic as geometry changes. The vectors for analysing are provided linear response time-dependent density functional theory (TDDFT) calculations under Tamm–Dancoff approximation. study photochemical CO ring opening oxirane an example and results corroborate traditional Gomer–Noyes mechanism derived experimentally. knowledge specific states reaction also agrees well with given previous theoretical work using TDDFT surface-hopping dynamics was validated high-quality quantum Monte Carlo calculations. QNTO useful considerably larger more complex systems: projecting those reference molecule, approach able identify analyse trans-2,3-diphenyloxirane molecule.