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Charge‐transfer transition energies and the prediction of reactivity in electrophile–nucleophile reactions
Author(s) -
Bethell Donald,
Parker Ver D.
Publication year - 1992
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.610050606
Subject(s) - chemistry , nucleophile , electrophile , charge (physics) , acceptor , transfer (computing) , computational chemistry , reactivity (psychology) , molecular physics , chemical physics , atomic physics , organic chemistry , catalysis , quantum mechanics , physics , medicine , alternative medicine , pathology , parallel computing , computer science
The differences between charge‐transfer transition energies calculated for donor‐acceptor pairs at infinite separation and values determined experimentally for the charge‐transfer complex geometry vary according to the charge type of the pairs and within a group of fixed charge type. It is argued that these differences provide a guide to the slope of the state‐correlation curves for the product configuration in electrophile‐nucleophile reactions of the corresponding charge type and that the observed variation invalidates the use of the simple expression Δ E = f Λ‐β with constant f , derived from the curve‐crossing model, to estimate energy barriers to reaction.