Rotational state specific dissociation dynamics of D2O via the C̃(010) state: The effect of bending vibrational excitation

Abstract

The rotational state resolved photodissociation dynamics of D2O via the [Formula: see text](010) state has been investigated by using the D-atom Rydberg tagging time-of-flight technique combined with a tunable vacuum ultraviolet light source. The D-atom action spectrum of the [Formula: see text](010) ← [Formula: see text](000) band and the corresponding time-of-flight (TOF) spectra of D-atom photoproducts formed following the excitation of D2O to individual rotational transition have been measured. By comparison with the action spectrum of the [Formula: see text](000) ← [Formula: see text](000) band, the bending vibrational constant of the [Formula: see text] state for D2O can be determined to be v2 = 1041.37 ± 0.71 cm−1. From the TOF spectra, the product kinetic energy spectra, the vibrational state distributions of OD products, and the state resolved anisotropy parameters have been determined. The experimental results indicate a dramatic variation in the OD product state distributions for different rotational excitations. This illuminates that there are two distinctive coupling channels from the [Formula: see text](010) state to the low-lying electronic states: the homogeneous electronic coupling to the Ã1B1 state, resulting in vibrationally hot OD(X) products, and the Coriolis-type coupling to the [Formula: see text]1A1 state, producing vibrationally cold but rotationally hot OD(X) and OD(A) products. Furthermore, the three-body dissociation channel is confirmed, which is attributed to the [Formula: see text] → 1A2 or [Formula: see text] → Ã pathway. In comparison with the previous results of D2O photolysis via the [Formula: see text](000) state, it is found that the v2 vibration of the parent molecule enhances both the vibrational and rotational excitations of OD products.