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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.
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: (2006-) created by M. Nic, J. Jirat, B. Kosata; updates compiled by A. Jenkins. ISBN 0-9678550-9-8.
Last update: 2014-02-24; version: 2.3.3.
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