A transparent interpretation of the relativistic contribution to the N.M.R. ‘heavy atom chemical shift’

Pekka Pyykkö; Andreas Görling; Notker Rösch

doi:10.1080/00268978700101071

A transparent interpretation of the relativistic contribution to the N.M.R. ‘heavy atom chemical shift’

Pekka Pyykkö
, Andreas Görling
, Notker Rösch

Associate Professorship of Theoretical Chemistry (2008 — 2024)

Research output: Contribution to journal › Article › peer-review

174 Scopus citations

Abstract

The N.M.R. chemical shift problem is formulated so that a correct nonrelativistic limit is obtained for the paramagnetic term using Extended Hückel level wavefunctions. Then the relativistic contributions are identified from a REX-EHT comparison in second-order perturbation theory. The results obtained for hydrogen halides, HX, agree with the observed experimental trend. The main mechanisms are the spin–orbit induced proton spin density in the π_1/2 MO and the spin–orbit induced Zeeman term in the 3σ MO. The results obtained for¹³C shifts in haloacetylenes and methyl halides are qualitatively correct, but too small. Possible reasons are discussed.

Original language	English
Pages (from-to)	195-205
Number of pages	11
Journal	Molecular Physics
Volume	61
Issue number	1
DOIs	https://doi.org/10.1080/00268978700101071
State	Published - May 1987

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abstract = "The N.M.R. chemical shift problem is formulated so that a correct nonrelativistic limit is obtained for the paramagnetic term using Extended H{\"u}ckel level wavefunctions. Then the relativistic contributions are identified from a REX-EHT comparison in second-order perturbation theory. The results obtained for hydrogen halides, HX, agree with the observed experimental trend. The main mechanisms are the spin–orbit induced proton spin density in the π1/2 MO and the spin–orbit induced Zeeman term in the 3σ MO. The results obtained for13C shifts in haloacetylenes and methyl halides are qualitatively correct, but too small. Possible reasons are discussed.",

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T1 - A transparent interpretation of the relativistic contribution to the N.M.R. ‘heavy atom chemical shift’

AU - Pyykkö, Pekka

AU - Görling, Andreas

AU - Rösch, Notker

PY - 1987/5

Y1 - 1987/5

N2 - The N.M.R. chemical shift problem is formulated so that a correct nonrelativistic limit is obtained for the paramagnetic term using Extended Hückel level wavefunctions. Then the relativistic contributions are identified from a REX-EHT comparison in second-order perturbation theory. The results obtained for hydrogen halides, HX, agree with the observed experimental trend. The main mechanisms are the spin–orbit induced proton spin density in the π1/2 MO and the spin–orbit induced Zeeman term in the 3σ MO. The results obtained for13C shifts in haloacetylenes and methyl halides are qualitatively correct, but too small. Possible reasons are discussed.

AB - The N.M.R. chemical shift problem is formulated so that a correct nonrelativistic limit is obtained for the paramagnetic term using Extended Hückel level wavefunctions. Then the relativistic contributions are identified from a REX-EHT comparison in second-order perturbation theory. The results obtained for hydrogen halides, HX, agree with the observed experimental trend. The main mechanisms are the spin–orbit induced proton spin density in the π1/2 MO and the spin–orbit induced Zeeman term in the 3σ MO. The results obtained for13C shifts in haloacetylenes and methyl halides are qualitatively correct, but too small. Possible reasons are discussed.

UR - https://www.scopus.com/pages/publications/0000225348

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JF - Molecular Physics

IS - 1

ER -

A transparent interpretation of the relativistic contribution to the N.M.R. ‘heavy atom chemical shift’

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