Analysis of Canonical Molecular Orbitals to Identify Fermi Contact Coupling Pathways. 1. Through-Space Transmission by Overlap of P-31 Lone Pairs

作者：Contreras Ruben H; Gotelli Gustavo; Ducati Lucas C; Barbosa Thais A; Tormena Claudio F^*

来源：Journal of Physical Chemistry A, 2010, 114(2): 1044-1051.

DOI：10.1021/jp908970f

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 it 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.

• 出版日期2010-1-21