Comparison of Autler-Townes splitting based absolute measurements of the (7)Li(2) A (1)Sigma(u) (+)-X (1)Sigma(g) (+) electronic transition dipole moment with ab initio theory

• Published in: The Journal of chemical physics 2008-11, Vol.129 (17), p.174301-174301
• Main Authors: Salihoglu, O, Qi, P, Ahmed, E H, Kotochigova, S, Magnier, S, Lyyra, A M
• Format: Article
• Language: English
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.3000416

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.