ISSN:
0020-7608
Keywords:
Computational Chemistry and Molecular Modeling
;
Atomic, Molecular and Optical Physics
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Intensities of a1Δg←X 3∑g- and b 1∑g+ ← X 3∑g- transitions in molecular oxygen have been calculated on the basis of the INDO method taking into account spin-orbit coupling by perturbation theory. The transitions are magnetic dipole in nature. The first of them (a - X) steals its intensity from 3Πg-3∑g- and 1Πg-1Δg transitions, which are determined by the orbital angular-momentum operator. This source is not the principal one for the intensity of the second (b-X) transition. Its intensity is stolen principally from microwave transitions between spin sublevels of the ground 3∑g- state. The last source explains the large difference in intensities of the a-X and b-X transitions. Calculated oscillator strengths are in a good agreement with experiment. The same integrals that determine the intensity also determine the parameters of the spin Hamiltonian for the ground 3∑g- state. These parameters are in a good agreement with experiment also, showing the validity of the whole calculation. In a condensed phase the investigated transitions are enhanced by intermolecular exchange interaction. It is known that an external heavy atom (EHA) enhances the b-X transition of oxygen in solution, but does not influence the a-X transition. In the collision complex O2-EHA, which has a geometry without inversion symmetry, the microwave transitions between spin sublevels of the “3∑g-” state obtain electric-dipole moments, which are stolen from the charge-transfer transition. This mechanism explains the selective effect of EHA.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/qua.560170219
