ABSTRACT
This article considers the extent to which one can control the reactivity of atom-diatom systems through reactant polarisation. Three different limits for reactivity manipulation are defined: "absolute" limits that do not depend on the reaction dynamics but can only be obtained for particular combinations of quantum numbers, "unconstrained" limits that depend on dynamics but not on constraints imposed by any particular experimental setup, and "constrained" limits that depend on dynamics and also on the constraints imposed by a particular experimental setup. Methods for calculation of these limits are presented and applied to the benchmark F + H2 reaction. The variations of the maximum and minimum reactivity one can obtain are analysed in terms of reaction mechanisms and steric constraints. Tables listing the minimum and maximum values of angular momentum polarisation moments of rank up to 4, and integer and half-integer quantum numbers up to 5, are also presented.
ABSTRACT
The H+ +D2(v=0,j=0)-->HD+D + reaction has been theoretically investigated by means of a time independent exact quantum mechanical approach, a quantum wave packet calculation within an adiabatic centrifugal sudden approximation, a statistical quantum model, and a quasiclassical trajectory calculation. Besides reaction probabilities as a function of collision energy at different values of the total angular momentum, J, special emphasis has been made at two specific collision energies, 0.1 and 0.524 eV. The occurrence of distinctive dynamical behavior at these two energies is analyzed in some detail. An extensive comparison with previous experimental measurements on the Rydberg H atom with D2 molecules has been carried out at the higher collision energy. In particular, the present theoretical results have been employed to perform simulations of the experimental kinetic energy spectra.
ABSTRACT
The quantum (QM) scattering theory has been difficult to apply to the family of insertion reactions and the approximate quasiclassical trajectory (QCT) method or statistical calculations were mostly applied. In this Letter, we compare the experimental differential cross sections for the title insertion reaction with the results of QM and QCT calculations on an ab initio potential energy surface. The QM results reproduce well the crossed beam experiment, while a small, but significant, difference in the QCT ones points to quantum effects, possibly the occurrence of tunneling through the combined potential and centrifugal barrier.
