Abstract
A time-dependent, quantum reaction dynamics approach in full dimensional, six degrees of freedom was carried out to study the energy requirement on reactivity for the HBr + OH reaction with an early, negative energy barrier. The calculation shows both the HBr and OH vibrational excitations enhance the reactivity. However, even this reaction has a negative energy barrier, the calculation shows not all forms of energy are equally effective in promoting the reactivity. On the basis of equal amount of total energy, the vibrational energies of both the HBr and OH are more effective in enhancing the reactivity than the translational energy, whereas the rotational excitations of both the HBr and OH hinder the reactivity. The rate constants were also calculated for the temperature range between 5 to 500 K. The quantal rate constants have a better slope agreement with the experimental data than quasi-classical trajectory results.
Highlights
The title reaction HBr +OH →Br +H2O has attracted great interest with many experimental and theoretical studies during the past several decades
We carried out a 6DOF quantum reaction dynamics, time-dependent wave packet propagation approach to study the HBr +OH →Br +H2O reaction system on the potential energy surface (PES) developed by Bowman’s group
For the HBr +OH reaction system with a negative-early barrier, this study shows that not all forms of energy are equal in enhancing the reactivity
Summary
The title reaction HBr +OH →Br +H2O has attracted great interest with many experimental and theoretical studies during the past several decades. The comparison of the ICS ratios on the equal amount total energy indicates that the vibrational energy of HBr is more effective than translational energy on promoting the reactivity for this negative-barrier reaction.
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