The photodissociation of NO2 in the second absorption band: Ab initio and quantum dynamics calculations

摘要: Abstract The photodissociation of NO 2 in the second absorption band (217 nm) is investigated by electronic structure as well quantum mechanical and classical dynamics calculations. Potential energies are calculated for five lowest A′ states using internally contracted multi-reference configuration interaction method standard correlation consistent polarized quadruple zeta basis set. two N–O bond lengths O–N–O angle varied over wide ranges. Our calculations unambiguously verify that due to excitation state 3 (2 B C v ), which only with non-vanishing transition dipole moment this energy range. State correlates diabatically O( 1 D) + NO( Π), but it connects adiabatically ground-state product channel P) + NO( Π). In present study, we construct a three-dimensional potential surface (PES) one adiabatic state, A′, primarily focus on cross-section state. general form spectrum progression diffuse vibrational structures reproduced rotational distributions Π) also determined. predicted internal relatively narrow entire range – quantitative agreement experimental result dissociation at 226 nm, severe qualitative disagreement measurements near 202 nm.