Electron flow in reaction mechanisms - Revealed from first principles

Gerald Knizia*, Johannes E.M.N. Klein

*Bijbehorende auteur voor dit werk

OnderzoeksoutputAcademicpeer review

196 Citaten (Scopus)


The "curly arrow" of Robinson and Ingold is the primary tool for describing and rationalizing reaction mechanisms. Despite this approach's ubiquity and stellar success, its physical basis has never been clarified and a direct connection to quantum chemistry has never been found. Here we report that the bond rearrangements expressed by curly arrows can be directly observed in ab initio computations, as transformations of intrinsic bond orbitals (IBOs) along the reaction coordinate. Our results clarify that curly arrows are rooted in physical reality - a notion which has been challenged before - and show how quantum chemistry can directly establish reaction mechanisms in intuitive terms and unprecedented detail.

Originele taal-2English
Pagina's (van-tot)5518-5522
Aantal pagina's5
TijdschriftAngewandte Chemie - International Edition
Nummer van het tijdschrift18
StatusPublished - 27-apr-2015
Extern gepubliceerdJa

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