Mise au point. Theorie des effets de couplage vibronique multimodes. Probleme a 2 etats. Couplage vibronique mettant en jeu des modes et des etats degeneres. Effets du couplage vibronique multimodes en spectroscopie. Comportement statistique des niveaux d'energie vibroniques. Intersections coniques et evolution temporelle de la fluorescence

Multimode molecular dynamics beyond the Born-Oppenheimer approximation

Multimode Molecular Dynamics Beyond the Born‐Oppenheimer Approximation

Traditional spectroscopic analysis of the complex and irregular absorption spectrum of NO2 has provided a relatively small amount of information concerning the nature of the excited states. An extensive ab initio investigation has been undertaken, therefore, to provide a basis for interpretation of the experimental results. Multiconfiguration self‐consistent‐field (MC–SCF) wavefunctions have been computed for the low‐lying X 2A1, A 2B2, B 2B1, C 2A2, 4B2, 4A2, and 2Σ+g electronic states of NO2. The minima of the A 2B2, B 2B1, and C 2A2 states have all been found to be within 2 eV of the minimum of the X 2A1 ground state; for these states, C2v potential surfaces have been constructed for purposes of a spectral interpretation. The 4B2, 4A2, and 2Σ+g states are all more than 4 eV above the minimum of the ground state and have been examined in less detail. The study described here significantly improves on previous NO2 ab initio calculations in three important areas: (1) The double‐zeta‐plus‐polarization quality basis set is larger and more flexible; (2) the treatment of molecular correlation is more extensive; and (3) the electronic energies have been calculated for several different bond lengths and bond angles in each state. For the four lowest doublet states the following spectral data have been obtained: The ground state experimental constants are included in parentheses. The estimated accuracy of the various parameters is ±0.02 A for bond length, ±2° for bond angle, ±10% for the vibrational frequencies, ±0.10 D for dipole moments, and ±0.3 eV for the adiabatic excitation energies. An unusual feature has been found for the 2Σ+g state. The equilibrium geometry of this linear state has two unequal bond lengths of 1.20 A and 1.42 A and the inversion barrier is approximately 800 cm−1.

The electronic structure of nitrogen dioxide. I. Multiconfiguration self‐consistent‐field calculation of the low‐lying electronic states

The laser induced dispersed fluorescence spectra (L.I.D.F.S.) of jet cooled NO2 molecules in emission from 11 different vibronic levels located between 22 006 and 23 625 cm−1 was recorded. The corresponding variety of Franck–Condon accesses has allowed the observation of the complete set of the 191 lowest vibrational levels of the X 2A1 ground state, located up to 10 000 cm−1. The vibrational band origins were measured to within typically 0.3 cm−1, assigned (n1, n2, n3), and fitted with a 24 coefficient Dunham expansion giving a typical residual error of 0.5 cm−1. Furthermore, the vibrationless A 2B2 level has probably also been observed at 9737 cm−1. A perturbative model of the X 2A1–A 2B2 vibronic interaction has been used in order to calculate the energy shift of the high vibrational levels (around 10 000 cm−1) of the X 2A1 state.

Laser induced dispersed fluorescence spectra of jet cooled NO2: The complete set of vibrational levels up to 10 000 cm−1 and the onset of the X̃ 2A1–Ã 2B2 vibronic interaction

J.L. Hardwick

Papers

The 2B1 ← 2A1 system of nitrogen dioxide☆