Rotational and vibrational state distributions have been measured for the OH/OD(A2Σ+) fragment produced
by the photodissociation of H2O/D2O at a set of wavelengths in the 133−119 nm range that lead to excitation
of the B̃(1A1) state, either directly or through particular absorption features of the C̃B1 ← X̃1A1 and D̃1A1 ←
X̃1A1 Rydberg transitions. The experimental distributions are obtained from the AΣ+−X2Π fluorescence
spectra using a truncated single value decomposition method (TSVD). They are compared to distributions
calculated in a complete three-dimensional quantum mechanical treatment by using two sets of diabatic potential
energy surfaces obtained by Dobbyn and Knowles (DK) and by van Harrevelt and van Hemert (Leiden). The
measured vibrational branching ratios seem to be better accounted for by the former and the rotational
distributions by the latter. However, a more detailed analysis indicates that the DK surface would presumably
account for the experiment if the room-temperature rotational distribution of the parent water molecule were
introduced in the calculation. The experimental results are therefore interpreted as a confirmation of the more
direct and shorter-lived trajectories favored by the DK surface.
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