Statistical properties of quantum probability fluctuations in complex-forming chemical reactions

Abstract

The energy dependence of quantum complex-forming reaction probabilities is well known to involve sharp fluctuations, but little seems to be known about their amplitudes. We develop here, for triatomic reactions, an analytical approach of their statistical distribution. This approach shows that the fluctuation amplitudes mainly depend on the numbers of available quantum states in the reagent and product channels. Its predictions appear to be in good quantitative agreement with quantum scattering calculations for the prototypical reaction H + + H 2 .

The kinetics of X + H2 reactions (X = C(1D), N(2D), O(1D), S(1D)) at low temperature: recent combined experimental and theoretical investigations

“…This originates from the fact that the statistical models do not account for the correct Poisson distribution for S matrix element and possible incomplete quenching of the interferences. [54,55] However, as far as integral cross-sections or rate constants (of interest in the present work) are concerned, statistical approaches are expected to be valid.…”

Unveiling shape resonances in H + HF collisions at cold energies

“…[6][7][8] ) where the deep potential well can stabilize a myriad of quasi-bound states. 9 Very recently, Perreault et al measured the role that the initial alignment of HD plays in H 2 + HD collisions, which in the cold energy regime, is governed by a resonance at around 1 K. 10,11 Using quantum mechanical scattering calculations, it was possible to assign this resonance to a single partial wave (L=2) 12,13 and, to elucidate that, for a particular combination of initial and final states, this resonance could be controlled, vanishing for a suitable alignment of the HD internuclear axis. 14 In this manuscript, we turn our attention to the FH 2 system, one of the most widely studied systems in reaction dynamics both experimentally 2,15-20 and computaa) Electronic mail: pjambrina@usal.es b) Electronic mail: lgonsan@usal.es c) Electronic mail: manuel.lara@uam.es d) Electronic mail: menendez@quim.ucm.es e) Electronic mail: aoiz@quim.ucm.es tionally (see for example refs.…”