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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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Unimolecular reactions

Unimolecular reactions

(p.169) 7 Unimolecular reactions
Theories of Molecular Reaction Dynamics

Niels E. Henriksen

Flemming Y. Hansen

Oxford University Press

This chapter considers unimolecular reactions; photo-induced reactions, i.e. true unimolecular reactions; and reactions initiated by collisional activation, i.e. apparent unimolecular reactions where it is assumed that the time scales for activation and subsequent reaction are well separated. Elements of classical and quantum dynamical descriptions are discussed, including Slater theory and the quantum mechanical description of photo-induced reactions. Statistical theories aiming at the calculation of micro-canonical as well as canonical rate constants are discussed, including a detailed discussion of RRKM theory. It concludes with a discussion of femtochemistry, i.e. the observation and control of chemical dynamics using femtosecond pulses of electromagnetic radiation, focusing on the control of unimolecular reactions via the interaction with coherent light, that is, laser control.

Keywords:   photo-induced reaction, collisional activation, dynamical theory, Slater theory, statistical theory, RRKM theory, micro-canonical rate constant, canonical rate constant, femtosecond chemistry, laser control

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