Global deperturbation analysis from energetic, magnetic, and radiative measurements: Application to Te2

Abstract

In the framework of a unified physical model, employed as a basis Hund’s case ‘‘c,’’ a quantitative description has been worked out for experimental data of term values, g factors, and lifetimes of excited B0+u and A1u states, as well as for relative intensities in B0+u–X0+g, A1u–X1g, and B0+u–X1g transitions. The model includes a minimum number of adjustable fitting parameters: deperturbed molecular constants for both states, intramolecular interaction matrix element (η), two electronic matrix elements of magnetic interactions (Gz,G±), as well as two parallel (Re∥B0u+–X0g+, Re∥A1u–X1g) and two perpendicular (Re⊥B0u+–X1g, Re⊥A1u–X0g+) electronic transition moments. The B0+u state g factors and the intensity distribution over P, R, Q branches in B0+u–X1g transition was found to be most sensitive to weak heterogeneous (ΔΩ=±1) perturbations, and a simple analytic connection between those characteristics has been proposed. The Ω-doubling constant for A1u state levels was evaluated. By transforming the responsible electronic matrix elements to Hund’s case ‘‘a’’ basis, the A1u state has been found to be basically a 3Σ1 component of the B 3Σ−u state, with a small admixture (<14%) of a 3Π1 component of the A 3Πu state, and a change in term notation from A1u to B1u is proposed.