Femtochemistry of bimolecular reactions from weakly bound complexes: computational study of the H + H′OD → H′OH + D or HOD + H′ exchange reactions

Abstract

A full-dimensional wavepacket propagation describing the bimolecular exchange reactions H + H′OD → H′OH + D or HOD + H′ initiated by photolysis of HCl in the hydrogen-bound complex (HCl)⋯(HOD) is reported. The dynamics of this reaction is carried out with the MCTDH method on an ab initio potential energy surface (PES) of H₃O and the initial state is derived from the ground state wavefunction of the complex obtained by relaxation on its own electronic ground state ab initio PES. The description of the system makes use of polyspherical coordinates parametrizing a set of Radau and Jacobi vectors. The calculated energy- and time-resolved reaction probabilities show, owing to the large collision energies at play stemming from the (almost full) photolysis of HCl, that the repulsion between oxygen in the H′OD molecule and the incoming hydrogen atom is the main feature of the collision and leads to non-reactive scattering. No abstraction reaction products are observed. However, both exchange processes are still observable, with a preference in O–H′ bond dissociation over that of O–D. The selectivity is reversed upon vibrational pre-excitation of the O–D stretching mode in the H′OD molecule. It is shown that, after the collision, the hydrogen atom of HCl does most likely not encounter the almost stationary chlorine atom again but we also consider the limit case where the H atom is forced to collide multiple times against H′OD as a result of being pushed back by the Cl atom.