Molecular transition moment determination by Autler-Townes spectroscopy: D 1Πu-E,F 1Σg+ bands of H2

Abstract We investigate theoretically the determination of vibronic transition moments between two electronic states of a molecule by using the Autler-Townes effect (also known as ac, optical or dynamical Stark splitting) in a double optical resonance experiment. We calculate the Autler-Townes spectra of some representative bands of H 2 (D 1 Π u -E,F 1 Σ g + ) and examine their dependences on laser detuning, intensity, bandwidth, and the Doppler effect. As input to our calculation, the D-E,F electronic transition moment and the (ν′=0–15, ν=3, 6 and 7) vibronic transition moments have been computed. Our investigation shows that with moderate laser requirement, the Autler-Townes splitting of a large number of D-E,F vibronic transitions in H 2 should be observable so that their transition moments may be deduced experimentally.