A scaling rule for molecular electronic transition dipole moments: application to asymptotically allowed and forbidden transitions

摘要

Guided by the work of Woerdman and Monyakin, we propose rules that allow the electronic transition dipole moment for a transition in one molecule to be determined from that of a similar one in an isovalent species. The rule can be applied to asymptotically allowed and forbidden transitions. We have tested it by applying it in two specific cases: the moments for the A ~1sum -> X ~1xum and X ~1sum -> B ~1PI transitions in Na_2 are found from those in Li_2, which are asymptotically allowed and the moments for the B-> X transition in O_2, Se_2, and Te_2 which are asymptotically forbidden, are found from moment data for S_2. Transition moments calculated with this rule are within 15 of the available literature values and behavior as a function of internuclear separation is well described.