State‐Resolved Stereodynamics of an Insertion Reaction O(1D2) + H2(v = 0, j) → OH(X2Πi; v′, N′, f′) + H

Abstract

AbstractThe product state‐resolved stereodynamics of the reaction of O(1D2) with H2 have been studied at 300 K at a mean collision energy of ca. 12 kJ mol−1, using polarized, Doppler‐resolved laser‐induced fluorescence to probe the scattered products, OH(X2Πi; v′ = 0, N′, f′), and polarized photodissociation of N2O to provide the reagent O(1D2) atoms. Product state‐resolved differential cross sections, rotational polarizations, and excitation functions are in very good qualitative agreement with the results of quasi‐classical trajectory (QCT) calculations, conducted on the Schinke‐Lester, SL1 ab initio potential energy surface (PES) for the ground electronic state of the collision complex. The experimental and computational results are compared with those obtained in a complementary study of the reaction of O(1D2) with CH4 and remarkable parallels have been exposed. The linear and angular momentum vector correlations are all consistent with an “insertion” mechanism, proceeding over an attractive PES, which presents no entrance barrier.