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ERIC Number: EJ1442697
Record Type: Journal
Publication Date: 2022-Nov
Pages: 11
Abstractor: As Provided
ISBN: N/A
ISSN: ISSN-0021-9584
EISSN: EISSN-1938-1328
"Physiker" versus "Organiker" Views of Reaction "Mechanism": How Natural Resonance Theory Bridges the Gap
Eric D. Glendening; Steven D. Burke; John W. Moore; Frank Weinhold
Journal of Chemical Education, v99 n11 p3702-3712 2022
Traditional physical chemistry conceptions of reaction mechanism are formulated in terms of stationary points of an Arrhenius-style "energy profile" that differs sharply (in purpose and form) from the corresponding Robinson-style "arrow-pushing" mechanistic conceptions of organic chemistry. We show here how these diverse "mechanistic" conceptions can be reconciled in a unified computational protocol based on a natural resonance theoretic (NRT) description of successive "bond shifts" between reactant and product bonding patterns. For pedagogical purposes, we employ a model S[subscript N]2 halide exchange reaction described at a routine level of density functional theory, but the outlined NRT protocol involves no intrinsic dependence on theory level, reaction order, or perceived "elementary" character of the reaction. The NRT-based characterization of electronic bond-shifts provides a rigorous criterion for judging the correctness of a proposed arrow-pushing mechanism, while also adding rich details of the multiple electronic "transitions" that may accompany a chemical transformation along the reaction pathway, even if the associated energy profile is barrierless or marked by a single maximal "transition state" feature.
Division of Chemical Education, Inc. and ACS Publications Division of the American Chemical Society. 1155 Sixteenth Street NW, Washington, DC 20036. Tel: 800-227-5558; Tel: 202-872-4600; e-mail: eic@jce.acs.org; Web site: http://pubs.acs.org/jchemeduc
Publication Type: Journal Articles; Reports - Descriptive
Education Level: N/A
Audience: N/A
Language: English
Sponsor: N/A
Authoring Institution: N/A
Grant or Contract Numbers: N/A