Vibronic coupling in the energetically six lowest electronic states of oxirane radical cation.

Multi-dimensional quantum mechanical simulations are carried out to understand the multi-state and multi-mode vibronic interactions in the first six low-lying viz., X ̃ 2 B 1 , A ̃ 2 A 1 , B ̃ 2 B 2 , C ̃ 2 A 2 , D ̃ 2 A 1 , and E ̃ 2 B 1 electronic states of c-C₂H₄O^·+. Vibronic coupling theory is applied to study interactions among electronic states using symmetry selection rules. A model 6 × 6 diabatic electronic Hamiltonian is constructed. The parameters of the diabatic Hamiltonian are estimated by performing extensive ab initio electronic structure calculations, using the EOM-IP-CCSD method. The nuclear dynamics calculations are performed with both time-independent and time-dependent quantum mechanical methods. The calculated vibronic structures of six electronic states are found to be in excellent agreement with the available experimental findings. Progressions found in the theoretical spectrum are assigned in terms of vibrational modes. It is found that extremely strong vibronic interactions among the X ̃ 2 B 1 – A ̃ 2 A 1 , B ̃ 2 B 2 – C ̃ 2 A 2 , and D ̃ 2 A 1 – E ̃ 2 B 1 electronic states results into highly overlapping vibronic bands due to multiple multi-state conical intersections. The impact of associated nonadiabatic effects on the vibronic structure and dynamics of the mentioned electronic states is examined at length. Interesting comparison is made with the results obtained for the isomeric acetaldehyde radical cation. [ABSTRACT FROM AUTHOR]