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.
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.
Giribet
Claudia G
CG
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
Ruiz de Azúa
Martín C
MC
D000465:Algorithms; D003903:Deuterium / Q000737:chemistry*; D004583:Electrons; D006859:Hydrogen / Q000737:chemistry*; D006860:Hydrogen Bonding; D009682:Magnetic Resonance Spectroscopy; D008956:Models, Chemical
D006859:Hydrogen; D003903:Deuterium