Premium
Investigation of the resonance‐assisted hydrogen bond in model β ‐diketones through localized molecular orbital analysis of the spin–spin coupling constants related to the O–H · · · O hydrogen bond
Author(s) -
Zarycz M. Natalia C.,
Provasi Patricio F.
Publication year - 2015
Publication title -
magnetic resonance in chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.483
H-Index - 72
eISSN - 1097-458X
pISSN - 0749-1581
DOI - 10.1002/mrc.4152
Subject(s) - chemistry , fermi contact interaction , delocalized electron , resonance (particle physics) , coupling constant , electron paramagnetic resonance , spin (aerodynamics) , bond order , dipole , spin polarization , molecular orbital , atomic physics , electron , condensed matter physics , paramagnetism , nuclear magnetic resonance , bond length , crystallography , molecule , quantum mechanics , physics , thermodynamics , organic chemistry , crystal structure
The resonance‐assisted hydrogen bond (HB) phenomenon has been studied theoretically by a localized molecular orbital (LMO) decomposition of the spin–spin coupling constants between atoms either involved or close to the O–H · · · O system of some β ‐diketones and their saturated counterparts. The analysis, carried out at the level of the second‐order polarization propagator approximation, shows that the contributions in terms of LMO to the paramagnetic spin orbital and the spin dipolar Ramsey terms proof the importance of the delocalized π ‐electron structure supporting the idea of the existence of the resonance‐assisted HB phenomenon phenomenon. The LMO contributions to the Fermi contact term indicate mainly the presence of the HB that may or not be linked to the π ‐electrons. Copyright © 2014 John Wiley & Sons, Ltd.