Theoretical Molecular Transition Probabilities. I. The V–N Transition in H2

Publisher Website
Google Scholar
Abstract
Theoretical investigation of the oscillator strength of the V–N transition in H2 has been carried out employing the alternative length, velocity, and acceleration operator methods in the calculations. By successive improvements in the approximate molecular wave functions assumed for the two states, convergence of the results obtained by the three methods toward a unique f value is demonstrated. The best wave functions employed yield an f value of 0.27 for the V–N transition in H2. Because in general the three methods weight different spatial portions of the wave functions in the dipole strength integrals, comparison of the alternative numerical f values is shown to provide some insight into the goodness, over‐all and regional, of these wave functions. Agreement among the three values is also shown to be a more sensitive test of the goodness of the wave functions than are the usual energy criteria. All integrals necessary in these computations are shown to be expressible in terms of Cαβγδε functions which are to be found in the literature. A systematic scheme for computing the oscillator strengths of any Σ—Σ transition involving one and two quantum‐number Slater orbitals in terms of these C functions is outlined.

This publication has 16 references indexed in Scilit: