CLOPPA-IPPP analysis of electronic mechanisms of intermolecular (1h)J(A,H) and (2h)J(A,D) spin-spin coupling constants in systems with D-H...A hydrogen bonds

Claudia G Giribet; Martín C Ruiz de Azúa

doi:10.1021/jp053492g

CLOPPA-IPPP analysis of electronic mechanisms of intermolecular (1h)J(A,H) and (2h)J(A,D) spin-spin coupling constants in systems with D-H...A hydrogen bonds

J Phys Chem A. 2005 Dec 29;109(51):11980-8. doi: 10.1021/jp053492g.

Authors

Claudia G Giribet¹, Martín C Ruiz de Azúa

Affiliation

¹ Department of Physics, Facultad de Ciencias Exactas y Naturales, University of Buenos Aires, Ciudad Universitaria, Pab. I, (1428) Buenos Aires, Argentina. giribet@df.uba.ar

PMID: 16366652
DOI: 10.1021/jp053492g

Abstract

The electronic origin of intermolecular (2h)J(A,D) and (1h)J(A,H) couplings is discussed by means of the CLOPPA-IPPP approach in several model complexes with D-H...A hydrogen bonds. It is found that the origin of these couplings is mainly due to the interaction between the acceptor sigma lone pair and vacant molecular orbitals localized in the D-H...A moiety, regardless of the donor and acceptor nuclei. The problem of the larger absolute value of (2h)J(A,D) compared to (1h)J(A,H) is also addressed.

Publication types

Research Support, Non-U.S. Gov't

MeSH terms

Algorithms
Deuterium / chemistry*
Electrons
Hydrogen / chemistry*
Hydrogen Bonding
Magnetic Resonance Spectroscopy*
Models, Chemical*

Substances

Hydrogen
Deuterium