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Theories of Molecular Reaction DynamicsThe Microscopic Foundation of Chemical Kinetics$
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Niels E. Henriksen and Flemming Y. Hansen

Print publication date: 2008

Print ISBN-13: 9780199203864

Published to Oxford Scholarship Online: January 2010

DOI: 10.1093/acprof:oso/9780199203864.001.0001

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Potential energy surfaces

Potential energy surfaces

(p.35) 3 Potential energy surfaces
Theories of Molecular Reaction Dynamics

Niels E. Henriksen

Flemming Y. Hansen

Oxford University Press

This chapter discusses potential energy surfaces, that is, the electronic energy as a function of the internuclear coordinates as obtained from the electronic Schrödinger equation. It focuses on the general topology of such energy surfaces for unimolecular and bimolecular reactions. To that end, concepts like saddle point, barrier height, minimum-energy path, and early and late barriers are discussed. It concludes with a discussion of approximate analytical solutions to the electronic Schrödinger equation, in particular, the interaction of three hydrogen atoms expressed in terms of Coulomb and exchange integrals, as described by the so-called London equation. From this equation it is concluded that the total electronic energy is not equal to the sum of H-H pair energies. Finally, a semi-empirical extension of the London equation — the LEPS method — allows for a simple but somewhat crude construction of potential energy surfaces.

Keywords:   electronic Schrödinger equation, saddle point, barrier height, minimum-energy path, early barrier, late barrier, Coulomb integral, exchange integral, London equation, LEPS surface

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