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separability assumption

This expression refers to the assumption, essential to conventional transition-state theory, that the energy of the system may be expressed as the sum of components associated with different degrees of freedom. In transition-state theory it is assumed that the energy of the motion of the system through the dividing surface of the potential-energy surface is separable into various components. In many practical calculations it is assumed that the energy of the system is separable into electronic, vibrational, rotational and translational energy.
Source:
PAC, 1996, 68, 149 (A glossary of terms used in chemical kinetics, including reaction dynamics (IUPAC Recommendations 1996)) on page 186
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IUPAC. Compendium of Chemical Terminology, 2nd ed. (the "Gold Book"). Compiled by A. D. McNaught and A. Wilkinson. Blackwell Scientific Publications, Oxford (1997). XML on-line corrected version: http://goldbook.iupac.org (2006-) created by M. Nic, J. Jirat, B. Kosata; updates compiled by A. Jenkins. ISBN 0-9678550-9-8. doi:10.1351/goldbook.
Last update: 2014-02-24; version: 2.3.3.
DOI of this term: doi:10.1351/goldbook.S05611.
Original PDF version: http://www.iupac.org/goldbook/S05611.pdf. The PDF version is out of date and is provided for reference purposes only. For some entries, the PDF version may be unavailable.
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