The classical statistical theory of three-atom reactions governed by short-range forces: Energy transfers and recoil energy distribution

Abstract

When the nascent products of a three-atom reaction governed by chemical forces separate, energy transfers may occur between vibrational, rotational, and translational motions. In the first part of the paper, we show from quasiclassical trajectory calculations on a model potential energy surface that (a) the vibrational energy is adiabatic on average as usually assumed in statistical theories, (b) rotational-translational energy transfer mainly favors translational motion (as was initially suggested by Marcus), but that (c) this transfer is inefficient when the product atom is sufficiently light with respect to the other two. A qualitative analysis of these findings is proposed based on arguments differing from those of Marcus, and Quack and Troe. In the second part of the paper, we extend the classical statistical formalism proposed recently by ourselves, initially limited to reactions governed by long-range forces, to the present more general case of reactions involving tight transition states and for which energy transfers are inefficient. In such a case, energy distributions at the exit transition state and in the products are the same. We focus our developments on the recoil energy distribution. Agreement between our theoretical result and the quasiclassical trajectory approach is shown to be very satisfactory.