Effect of high pressure on the topography of potential energy surfaces

Author:

Spooner Jacob1,Smith Brandon2,Weinberg Noham12

Affiliation:

1. Department of Chemistry, Simon Fraser University, Burnaby, BC V5A 1S6, Canada.

2. Department of Chemistry, University College of the Fraser Valley, Abbotsford, BC V2S 7M8, Canada.

Abstract

Properties and reactivity of chemical compounds change dramatically at elevated pressures. Since kinetics and mechanisms of condensed-phase reactions are described in terms of their potential energy (PESs) or Gibbs energy (GESs) surfaces, chemical effects of high pressure can be assessed through analysis of pressure-induced deformations of GESs of solvated reaction systems. We discuss general trends expected for such changes and use quantum mechanical calculations to construct PESs of compressed species for hydrogen and methyl transfer reactions.

Publisher

Canadian Science Publishing

Subject

Organic Chemistry,General Chemistry,Catalysis

Reference76 articles.

1. aGlasstone, S.; Laidler, K. J.; Eyring, H. The Theory of Rate Processes: The Kinetics of Chemical Reactions, Viscosity, Diffusion and Electrochemical Phenomena; McGraw-Hill: New York; London, 1941;

2. Advances in Chemical Physics

3. Potential Energy Surfaces and Dynamics Calculations

4. dHirst, D. M. Potential Energy Surfaces: Molecular Structure and Reaction Dynamics; Taylor & Francis London: Philadelphia, 1985;

5. eHehre, W. J.; Radom, L.; von Schleyer, P. R.; Pople, J. Ab Initio Molecular Orbital Theory; Wiley: New York, 1986;

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