Quantum calculations of mode specificity in reactions of H with HOD and H2O

Abstract

We present approximate quantum calculations of cumulative reaction probabilities, rotationally averaged cross sections, and branching ratios for the reactions H+HOD and H+H2O, using the Walch–Dunning–Schatz–Elgersma potential. The calculations are done using the reduced dimensionality, adiabatic-bend approach in which the three internal bending degrees of freedom are treated adiabatically. The H+HOD calculations focus primarily on the effect of vibrationally exciting the OH or OD local modes of HOD on the reactivity, the branching ratios to form the products HD+OH and H2+OD, and their final vibrational state distributions. The calculations of the H+H2O reaction focus on two initial vibrational states, one with three quanta of vibrational excitation in the local mode stretch, and one with two quanta in one local mode and one quantum in the other local mode. The results are generally in good agreement with experiments and previous calculations.