title: Analysis of canonical molecular orbitals to identify fermi contact coupling pathways. 1. Through-space transmission by overlap of (31)P lone pairs.
abstract: In this work, a new approach to studying coupling pathways for the Fermi contact term of NMR spin-spin coupling constants (SSCCs) is presented. It is based on the known form of propagating the Fermi hole through a canonical molecular orbital (CMO). It requires having an adequate spatial description of the relevant canonical molecular orbitals, which are obtained by expanding CMOs in terms of natural bond orbitals (NBOs). For detecting the relevant contributions of CMOs to a given Fermi contact (FC) pathway, the description of the FC in terms of the triplet polarization propagator (PP) is used. To appreciate the potential of this approach, dubbed FCCP-CMO (Fermi contact coupling pathways-CMO), it is applied to analyze the through-space transmission of the FC term of J(PP) SSCCs by overlap of the P lone pairs. This method can be applied using well-known quantum chemistry software without any further modification, which makes it appealing for use as a complement to SSCC measurements by NMR spectroscopy.
authors.affiliation: Department of Physics, FCEyN, University of Buenos Aires, and CONICET, Buenos Aires, Argentina.
authors.forename: Rubén H
authors.initials: RH
authors.lastname: Contreras
authors.forename: Gustavo
authors.initials: G
authors.lastname: Gotelli
authors.forename: Lucas C
authors.initials: LC
authors.lastname: Ducati
authors.forename: Thais M
authors.initials: TM
authors.lastname: Barbosa
authors.forename: Cláudio F
authors.initials: CF
authors.lastname: Tormena
mesh_terms: D000465:Algorithms; D055598:Chemical Phenomena; D009682:Magnetic Resonance Spectroscopy / Q000379:methods; D008958:Models, Molecular; D008968:Molecular Conformation; D009943:Organophosphorus Compounds / Q000737:chemistry*; D010758:Phosphorus / Q000737:chemistry*; D017553:Phosphorus Compounds / Q000737:chemistry*; D011789:Quantum Theory
chemical_list: D009943:Organophosphorus Compounds; D017553:Phosphorus Compounds; D010758:Phosphorus