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Large Solvation Effect in the Optical Rotatory Dispersion of Norbornenone
Author(s) -
Lahiri Priyanka,
Wiberg Kenneth B.,
Vaccaro Patrick H.,
Caricato Marco,
Crawford T. Daniel
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201306339
Subject(s) - solvation , polarizable continuum model , polarizability , chemical physics , dispersion (optics) , chemistry , solvent effects , optical rotation , molecule , phase (matter) , density functional theory , cluster (spacecraft) , molecular physics , computational chemistry , solvent , physics , quantum mechanics , organic chemistry , computer science , programming language
The anomalously large chiroptical response of (1 R ,4 R )‐norbornenone has been probed under complementary vapor‐phase and solution‐phase conditions to assess the putative roles of environmental perturbations. Measurements of the specific rotation for isolated (gas‐phase) molecules could not be reproduced quantitatively by comprehensive quantum‐chemical calculations based on density‐functional or coupled‐cluster levels of linear‐response theory, which suggests that higher‐order treatments may be needed to accurately predict such intrinsic behavior. A substantial, yet unexpected, dependence of the dispersive optical activity on the nature (phase) of the surrounding medium has been uncovered, with the venerable Lorentz local‐field correction reproducing solvent‐mediated trends in rotatory dispersion surprisingly well, whereas more modern polarizable continuum models for implicit solvation performed less satisfactorily.