Spatial Correlations in Condensed Phase Reactions
Taylor & Francis
Spatial correlations among reacting species in condensed media result from an interplay of reaction (which tends to lead to negative correlations), replacement or dissociation (which tend to produce positive correlations), and diffusion (which tends to smooth correlations out). Where correlations are high associative reactions are generally rapid. Where they are low the associative reaction is generally diminished. These characteristics of condensed phase processes have important consequences in a wide range of situations. In this paper, I review several examples drawn from radiation-physics, -chemistry, and -biochemistry of how spatial correlations determine the kinetics of reaction. Utilizing this theme, I also present two new results. I discuss a model of defect production in collision cascades in which the collective excitations during the cooling of the cascade contribute to defect recombination. A quantitative comparison with experiment is made. Lastly, I show how the kinetics of a diffusion-limited reversible reaction differ from a model which tacitly assumes that the spatial correlations which prevail are those of the irreversible reaction. A connection is drawn between these models and the observed kinetics of thermal donor formation.
D. Peak, "Spatial Correlations in Condensed Phase Reactions," Radiation Effects 111&112, 309- 321 (1989).