Journal of Chemical Physics, Vol.115, No.14, 6450-6458, 2001
Split operator method for the nonadiabatic (J=0) bound states and (A <- X) absorption spectrum of NO2
A split operator three-dimensional wave packet propagation method is adapted for the determination of the bound states and absorption band shape of NO2 molecule presenting a conical intersection between its ground X (2)A(1) and first excited A B-2(2) electronic states. The numerical task, basically resting on a Fourier transform methodology, may present interesting advantages over matrix diagonalization techniques. The calculations of bound levels over a wide energy range and the absorption (A B-2(2)<--X(2)A(1)) band shape, extending up to 40000 cm(-1), are put on an equal footing by a nonadiabatic three-dimensional wave packet propagation using available ab initio potential energy surfaces. Good agreement is obtained when comparing the calculated absorption spectrum to experimental data in a low resolution limit. The position and amplitude of the band shape are determined within only 2 and 3% of relative error, respectively, the total width being still overestimated by about 15%. An analysis of the causes of errors is presented stressing the need for more accurate transition dipole moment determinations.