Time-resolved double-resonance spectroscopy: Lifetime measurement of the $6\,^1Σ_g^+(7,31)$ electronic state of molecular sodium

Abstract

We report on the lifetime measurement of the $6\,^1Σ_g^+ (7,31)$ state of Na$_2$ molecules, produced in a heat-pipe oven, using a time-resolved spectroscopic technique. The $6\,^1Σ_g^+ (7,31)$ level was populated by two-step two-color double resonance excitation via the intermediate $A\,^1Σ_u^+ (8,30)$ state. The excitation scheme was done using two synchronized pulsed dye lasers pumped by a Nd:YAG laser operating at the second harmonics. The fluorescence emitted upon decay to the final state was measured using a time-correlated photon counting technique, as a function of argon pressure. From this the radiative lifetime was extracted by extrapolating the plot to collision-free zero pressure. We also report calculated radiative lifetimes of the Na$_2$ $6\,^1Σ_g^+$ ro-vibrational levels in the range of $v=0-200$ with $J=1$ and $J=31$ using the LEVEL program for bound-bound and the BCONT program for bound-free transitions. Our calculations reveal the importance of the bound-free transitions on the lifetime calculations and a large difference of about a factor of three between the $J=1$ and $J=31$ for the $v=40$ and $v=100$, due to the wavefunction alternating between having predominantly inner and outer well amplitude.