Band strengths for electric dipole transitions from ab initio computation: Lio [formula omitted] AlO [formula omitted]

Abstract

Intensity relations in diatomic molecule spectra are reviewed and computationally useful expressions given for band strengths and band oscillator strengths in terms of electronic expectations values, which are the normal output of ab initio calculation. Calculations of these properties are reported for 7Li16O and 27Al16O. With very accurate [formula omitted] and A 2Σ+ LiO wavefunctions, band strengths and band oscillator strengths for all transitions involving ν,′ ν″ up to four are given, both within and between the electronic states. Results, given as band strengths (band oscillator strengths), are [formula omitted], [formula omitted]. A 2Σ+ −A 2Σ+ 0–1 band, [formula omitted] and [formula omitted], [formula omitted]. Similar data are presented for the X 2Σ+ and [formula omitted] states of 27Al16 0 using wavefunctions of comparable quality. The dipole moment in the X 2Σ+ state is shown to be essentially constant over the range of nuclear vibration in the lowest vibrational levels. Results, given as band strengths (band oscillator strengths), are X 2Σ+ − X 2Σ+ 0–1 band, [formula omitted], [formula omitted], [formula omitted]. Adjusting this last band oscillator strength by use of the observed rather than the computed energy separation of the X 2Σ+ and [formula omitted] states increases it from [formula omitted]. Finally more limited and less accurate calculations on the B 2Σ+ state of 27Al160, give the estimates B 2Σ+ − B 2Σ+ 0–1 band, [formula omitted] and X2 Σ+ − B 2Σ+ 0–0 band, 1.8 a.u. (0.07). © 1973, The American Institute of Physics. All rights reserved.