Critical analysis of the through-space transmission of NMR J(FH) spin-spin coupling constants

Autor(es)

Contreras, Ruben H. ; Ducati, Lucas C. ; Tormena, Claudio F.

• Tipo de documento: Artigo Científico
• Fonte: International Journal of Quantum Chemistry; v. 112, n. 19, p. 6-pg., 2012-10-05.

Resumo

NMR JFH coupling constants transmitted through space are known to show several unusual peculiarities. The main three are (a) in many cases their experimental values are reported to be positive and in others, negative; (b) theoretical values show that in some cases they are substantially contributed not only from the Fermi contact (FC) term but also from the paramagnetic spin orbit (PSO) term, and their respective signs could be either like or unlike; (c) in many cases it can hardly be expected that the corresponding F-H proximate interactions could be considered a hydrogen bond, whereas in other cases it is evident that they are. For discussing points (a) and (b), characteristics of both the FC and PSO terms are discussed performing qualitative analyses based on their expressions given in terms of the polarization propagator formalism. Point (c) is discussed in terms of the well-known Bader's QTAIM method as well as recalling the known relationship between the transmissions of the Fermi hole and of the FC interaction of spinspin coupling constants. (c) 2012 Wiley Periodicals, Inc. (AU)

• Processo FAPESP: 10/15765-4 - Estudo dos Mecanismos de Transmissão do Acoplamento Escalar J(FF) Spin-Spin através do Espaço
• Beneficiário: Lucas Colucci Ducati
• Modalidade de apoio: Bolsas no Brasil - Pós-Doutorado
• Processo FAPESP: 10/10993-9 - Estudo do mecanismo de transmissão de constantes de acoplamento escalar através do espaço
• Beneficiário: Claudio Francisco Tormena
• Modalidade de apoio: Auxílio à Pesquisa - Regular