Chemical reactions in condensed phases

Nor with a wise intelUgence imposed An order on themselves, nor in some pact Agreed what movements each should generate. 

Have always moved, since infinite time began. 

Are driven by collisions, are borne on By their own weight, in every kind of way Meet and combine, try every possible. 

Every conceivable pattern, till at length Experiment culminates in that array Which makes great things... 

Lucretius (c. 99-c. 55 bceJ The way things are translated by Rolfe Humphries, Indiana University Press, 1968 

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The scope of this book goes beyond the proper field of solvent effects on chemical reactions. It actually goes deeper in the analysis of solvent effects as such and of chemical reactions. It also addresses the problem of mimicking chemical reactions in condensed phases and bioenvironments. The authors have gone through the problems raised by the limitations found in the theoretical representations. In order to understand, it is not sufficient to have agreement with experiments, the schemes should meet the requirements put forward by well founded physical theories. 

STATISTICAL MECHANICAL MODELING OF CHEMICAL REACTIONS IN CONDENSED PHASE SYSTEMS... 

As pointed out already in [62], the mechanism in question could also have a crucial role in reactions in condensed phases where it should arise due to large amplitude oscillatoiy motions, like internal rotations or librations, of molecules or reactive atomic groups. Such oscillatoiy motion could be excited, e.g., by microwaves and the mechanism in question should thus be of great importance also for understanding microwave acceleration of chemical reactions in condensed phases. 

Kramers treatment of the escajje of a Brownian particle out of a potential welH" as a model for chemical reactions in condensed phases has played a central role in many areas of physics and chemistry. The original application to chemical reaction rates has in fact been disregarded by chemists until the last decade. Other applications were mostly in solid-state physics desorption... 

For recent reviews of theories of chemical reactions in condensed phases, see J. T. Hynes, in M. Baer (Ed.), The Theory of Chemical Reactions Dynamics, Chemical Rubber, Boca Raton, FL, 1986. 

Caratzoulas, S. and Schwartz, S.D. (2001). A computational method to discover the existence of promoting vibrations for chemical reactions in condensed phases. J. Chem. Phys. 114, 2910-2918... 

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