Multiconfigurational self-consistent field and multireference internally contracted configuration interaction studies on the excited states of weakly bonded NO2 dimer (N2O4)

摘要

In this paper, the vertical excitation energies of total of 32 states of N2O4 including the lowest two singlet states and two triplet states of each of the A(g), B-3u, B-2u, B-1g, B-1u, B-2g, B-3g, and A(u) symmetries were calculated at multiconfigurational self-consistent field (MCSCF) and the multireference internally contracted configuration interaction (MRCI) levels of theory on the active space (15o,16e) with aug-cc-pVDZ basis set. The potential energy curves of the eight singlet states(1 (1)A(g), 1 B-1(3u), 1 B-1(2u), 1 B-1(1g), 1 B-1(1u), 1 B-1(2g), 1 B-1(3g), and 1 (1)A(u)) and eight triplet states (1 (3)A(g), 1 B-3(3u), 1 B-3(2u), 1 B-3(1g), 1 B-3(1u), 1 B-3(2g), 1 B-3(3g), and 1 (3)A(u)) were calculated at MCSCF and MRCI levels of theory on the active space (15o,16e) with aug-cc-pVDZ basis set along the N-N distance. The vertical excitation energies of 1 B-1(3u), 1 B-1(2u), and 1 B-1(1u) states with nonzero transition moment are 4.60 eV (269.6 nm), 6.06 eV (204.6 nm), and 7.71 eV (160.8 nm), respectively, at MRCI level of theory. The photodissociation asymptotics were assigned as NO2(X (2)A(1))+NO2(X (2)A(1)) for ground state 1 (1)A(g) and the 1 B-3(1u) state, NO2(X (2)A(1))+NO2(1 (2)A(2)) for the 1 B-1(1g), 1 B-3(1g), 1 (1)A(u), and 1 (3)A(u) states, NO2(X (2)A(1))+NO2(1 B-2(1)) for the 1 B-1(3u), 1 B-3(3u), 1 B-1(2g), and 1 B-3(2g) states, and NO2(X (2)A(1))+NO2(1 B-2(2)) for the 1 B-1(2u), 1 B-3(2u), 1 B-1(3g), and 1 B-3(3g) states. (c) 2007 American Institute of Physics.