Photodissociation dynamics of H2O: Effect of unstable resonances on the $\tilde B\,^{1}{\rm \!A}_{1}$B̃1A1 electronic state

Abstract

We report a tunable vacuum ultraviolet photodissociation study of H(2)O from different unstable resonances in the B̃(1)A(1) electronic state, using the H-atom Rydberg tagging technique. The quantum state resolved OH product translational energy distributions and angular distributions have been measured. Experimental results illustrate, for the first time, that excitation to the different unstable resonances has very different effect on the OH(X) and OH(A) product channels. The OH(X) product rotational distributions vary only slightly, while the OH(A) product rotational distributions and state-resolved angular distributions change dramatically as the photolysis energy increases. Effect of parent rotational excitation on the OH(A) product has also been observed. Through careful simulations to the experimental spectra, OH(A)∕OH(X) branching ratios have been determined at five photolysis wavelengths. The general agreement between theory and experiment in the branching ratios is good. The branching ratios for the OH(A) product from different parent rotational levels are close to the nuclear spin-statistics value, which is also consistent with the extremely low rotational temperature of the H(2)O beam in the current experiment.