Comparison of Autler–Townes splitting based absolute measurements of the L7i2 A Σ1u+−X Σ1g+ electronic transition dipole moment with ab initio theory

Abstract

We report a comparison between experimental and theoretical electronic transition dipole moment values for the (7)Li(2) A (1)Sigma(u) (+)-X (1)Sigma(g) (+) system. The experimental results are based on measuring the absolute magnitude of the transition dipole matrix elements from Autler-Townes splitting of rovibrational transitions for different R-centroid values. The ab initio theoretical calculations of the transition dipole moment for the (7)Li(2) A (1)Sigma(u) (+)-X (1)Sigma(g) (+) system were performed using two different quantum-mechanical models: an all-electron valence bond self-consistent-field method and a pseudopotential molecular orbital method. As expected for the smallest molecule with core electrons, the agreement between experiment and theory is very good.