Assignment of excited-state bond lengths using branching-ratio measurements: The B${}^2{\Sigma }^{+}$ state of BaH molecules

Abstract

Vibrational branching ratios in the B${}^2{\Sigma }^{+}$ -- X${}^2{\Sigma }^{+}$ and A${}^2\Pi$ -- X${}^2{\Sigma }^{+}$ optical-cycling transitions of BaH molecules are investigated using measurements and {\it ab initio} calculations. The experimental values are determined using fluorescence and absorption detection. The observed branching ratios have a very sensitive dependence on the difference in the equilibrium bond length between the excited and ground state, $\Delta r_e$: a 1 pm (.5\%) displacement can have a 25\% effect on the branching ratios but only a 1\% effect on the lifetime. The measurements are combined with theoretical calculations to reveal a preference for a particular set of published spectroscopic values for the B${}^2{\Sigma }^{+}$ state ($\Delta r_e^{B-X}$ = +5.733 pm), while a larger bond-length difference ($\Delta r_e^{B-X}=6.3-6.7$ pm) would match the branching-ratio data even better. By contrast, the observed branching ratio for the A${}^2{\Pi }_{3/2}$ -- X${}^2{\Sigma }^{+}$ transition is in excellent agreement with both the {\it ab initio} result and the spectroscopically measured bond lengths. This shows that care must be taken when estimating branching ratios for molecular laser cooling candidates, as small errors in bond-length measurements can have outsize effects on the suitability for laser cooling. Additionally, our calculations agree more closely with experimental values of the B${}^2{\Sigma }^{+}$ state lifetime and spin-rotation constant, and revise the predicted lifetime of the H${}^2\Delta$ state to 9.5 $\mu$s.