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Direct ab initio dynamics studies on the hydrogen‐abstraction reactions of OH radicals with HOX (X = F, Cl, and Br)

The hydrogen abstract reactions of OH radicals with HOF (R1), HOCl (R2), and HOBr (R3) have been studied systematically by a dual‐level direct‐dynamics method. The geometries and frequencies of all the stationary points are optimized at the MP2/6‐311+G(2d, 2p) level of theory. A hydrogen‐bonded complex is located at the product channel for the OH + HOBr reaction. To improve the energetics information along the minimum energy path (MEP), single‐point energy calculations are carried out at the CCSD(T)/6‐311++G(3df, 3pd) level of theory. Interpolated single‐point energy (ISPE) method is employed to correct the energy profiles for the three reactions. It is found that neither the barrier heights (ΔE) nor the H—O bond dissociation energies [D(H—O)] exhibit any clear‐cut linear correlations with the halogen electronegative. The decrease of ΔE and D(H—O) for the three reactions are in order of HOF > HOBr > HOCl. Rate constants for each reaction are calculated by canonical variational transition‐state theory (CVT) with a small‐curvature tunneling correction (SCT) within 200–2000 K. The agreement of the rate constants with available experimental values for reactions R2 and R3 at 298 K is good. Our results show that the variational effect is small while the tunneling correction has an important contribution in the calculation of rate constants in the low‐temperature range. Due to the lack of the kinetic data of these reactions, the present theoretical results are expected to be useful and reasonable to estimate the dynamical properties of these reactions over a wide temperature range where no experimental value is available. © 2004 Wiley Periodicals, Inc. J Comput Chem 25: 558–564, 2004