The influence of interactions between reagents on the excess in the rate of quenching reaction: Molecular dynamics study

Litniewski, Marek
July 2007
Journal of Chemical Physics;7/21/2007, Vol. 127 Issue 3, p034505
Academic Journal
The influence of the interactions between reagents on the excess in the rate coefficient, Δk, for the instantaneous reaction A+B→C+B have been investigated by performing large scale molecular dynamics simulations for simple soft spheres. The simulation method has enabled us to determine the contributions to Δk coming from A-B as well as B-B interactions. The simulations have shown that positive values of Δk that appear both for the liquid and for the Brownian system [M. Litniewski, J. Chem. Phys. 123, 124506 (2005); 124, 114501 (2006)] result from B-B interactions. If B-B interactions were absent, Δk was always negative. The influence of B-B interactions was about three times higher for the Brownian system than for the liquid. A qualitative explanation for the effect has been proposed basing on a simple model and analyzing the influence of B-B interactions on fluctuations in concentrations of reagents. The influence of A-B interactions was completely negligible except for the liquid at short times, for which the cancellation of A-B interaction noticeably decreased Δk.


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