Statistical analysis of the computed (X)over-tilde(2)A(1)/(A)over-tilde(2)B(2) spectrum of NO2: Some insights into the causes of its irregularity

摘要

We present a statistical analysis of the B-2 symmetry lines of the nonadiabatic (X)over-tilde(2)A(1)/(A)over-tilde(2)B(2) spectrum of NO2 in the energy range 10000-22000 cm(-1), obtained by ab initio diabatic potentials refined with respect to the experimental lines until 10000 cm(-1). The two most common statistical measures, the nearest neighbor spacing distribution and the (delta)over-bar(3) are taken into account. Both the statistics show a high degree of irregularity of the spectrum. The analysis is repeated in restricted ranges for which analogous investigations on experimental data are reported in the literature. The comparison is always satisfactory. Comparison is also discussed with respect to previous theoretical results obtained by other authors. We investigate the causes of the spectrum irregularity by removing systematically some selected couplings from the full nonadiabatic Hamiltonian. We find that the irregularity is due to two main causes; the sensible vibronic coupling between the two diabatic states (X)over-tilde(2)A(1) and (A)over-tilde(2)B(2) and the stretch-bend couplings on the diabatic ground surface (X)over-tilde(2)A(1). (C) 1998 American Institute of Physics. [References: 24]