The anisotropy of the nuclear spin–spin coupling tensor, relative to P, H and H, H interacting nuclei, has been investigated by means of extended ab initio calculations in the molecules PH<sup> - </sup><sub>2</sub>, PH3, and PH<sup> + </sup><sub>4</sub>. The coupled Hartree–Fock perturbed scheme has been employed retaining the nonrelativistic Ramsey Hamiltonians. The most important contributions to the anisotropy in the P, H coupling arise from the Fermi contact-spin-dipolar cross term, which is partially counterbalanced by the spin-orbit effect. The discrepancies emerging between computed and experimental J(P,H) in phosphine and phosphonium are interpreted in terms of neglected electron correlation contributions. A dramatic sensitivity of the Fermi contact term of the molecular geometry has been found for PH<sub>2</sub><sup> - </sup>. The calculations show that the P–H coupling is more anisotropic than N–H, which is seemingly due to the enhanced nonsphericity of electron distribution.

Anisotropy of the nuclear spin coupling in PH_2-, PH_3, and PH_4+ molecules / Lazzeretti, Paolo; E., Rossi; F., Taddei; R., Zanasi. - In: THE JOURNAL OF CHEMICAL PHYSICS. - ISSN 0021-9606. - STAMPA. - 77:(1982), pp. 408-414}.

Anisotropy of the nuclear spin coupling in PH_2-, PH_3, and PH_4+ molecules.

LAZZERETTI, Paolo;
1982-01-01

Abstract

The anisotropy of the nuclear spin–spin coupling tensor, relative to P, H and H, H interacting nuclei, has been investigated by means of extended ab initio calculations in the molecules PH - 2, PH3, and PH + 4. The coupled Hartree–Fock perturbed scheme has been employed retaining the nonrelativistic Ramsey Hamiltonians. The most important contributions to the anisotropy in the P, H coupling arise from the Fermi contact-spin-dipolar cross term, which is partially counterbalanced by the spin-orbit effect. The discrepancies emerging between computed and experimental J(P,H) in phosphine and phosphonium are interpreted in terms of neglected electron correlation contributions. A dramatic sensitivity of the Fermi contact term of the molecular geometry has been found for PH2 - . The calculations show that the P–H coupling is more anisotropic than N–H, which is seemingly due to the enhanced nonsphericity of electron distribution.
77
408
414}
Anisotropy of the nuclear spin coupling in PH_2-, PH_3, and PH_4+ molecules / Lazzeretti, Paolo; E., Rossi; F., Taddei; R., Zanasi. - In: THE JOURNAL OF CHEMICAL PHYSICS. - ISSN 0021-9606. - STAMPA. - 77:(1982), pp. 408-414}.
Lazzeretti, Paolo; E., Rossi; F., Taddei; R., Zanasi
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11380/454510
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