The normal range for secondary Swain-Schaad exponents without tunneling or kinetic complexity. Academic Article

abstract

• An analysis is presented of the range of secondary Swain-Schaad exponents to be expected at 25 degrees C in the absence of tunneling or kinetic complexity. From 15 996 sets of exact harmonic semiclassical equilibrium isotope effects for simple C-H/D/T exchange reactions and 954 sets of exact harmonic semiclassical secondary H/D/T kinetic isotope effects for C-H positions in simple organic reactions, the distribution of Swain-Schaad exponents versus magnitude of the isotope effect is determined. This distribution defines when a secondary Swain-Schaad exponent may be considered to implicate nonsemiclassical behavior, revises the expected Swain-Schaad exponent for extrapolation of secondary isotope effects, and serves as a guide to the uncertainty in such extrapolations.

authors

• Singleton, Daniel

author list (cited authors)

• Hirschi, J., & Singleton, D. A

citation count

• 32

complete list of authors

• Hirschi, Jennifer||Singleton, Daniel A

publication date

• January 2005

publisher

• American Chemical Society (ACS)  Publisher

published in

• Journal of the American Chemical Society  Journal

keywords

• Hydrogen
• Kinetics
• Models, Chemical
• Quantum Theory

PubMed Central ID

• 15755143

Digital Object Identifier (DOI)

• 10.1021/ja0430752

start page

• 3294

end page

• 3295

volume

• 127

issue

• 10

URL

• http%3A%2F%2Fdx.doi.org%2F10.1021%2Fja0430752