The visible absorption spectrum of NO2: A three-mode nuclear dynamics investigation

The vibronic band origins of the visible absorption spectrum of NO₂ are calculated theoretically with the aid of a simple model Hamiltonian for the coupled electronic and vibrational motions. Including all three vibrational modes in the calculation and using ab initio values of the relevant parameters, we obtain satisfactory qualitative agreement with experiment. In particular, the observed high density and irregular intensity distribution of the band origins is reproduced correctly by the calculation. The present results confirm unambiguosly that the anomalous vibronic structure of the ${}^2\text{B}{}_2\text{←}{}^2\text{A}{}_1$ transition is caused by strong nonadiabatic interactions between the ²B₂ and ²A₁ electronic states of NO₂. They also show that simple deconvolution procedures, which are often used to deperturb irregular spectra, are not applicable to the ${}^2\text{B}{}_2\text{←}{}^2\text{A}{}_1$ transition of NO₂. To further explore the strength of the nonadiabatic effects in NO₂, we calculate the mixing of the different electronic species in the vibronic eigenstates and compare it to several relevant experimental quantities.