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

165 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

Access to Document

10.1080/00268978700101071

Cite this

@article{ec4a2f443f7f4108aff7f39ab5fe4cf5,

title = "A transparent interpretation of the relativistic contribution to the N.M.R. {\textquoteleft}heavy atom chemical shift{\textquoteright}",

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.",

author = "Pekka Pyykk{\"o} and Andreas G{\"o}rling and Notker R{\"o}sch",

year = "1987",

month = may,

doi = "10.1080/00268978700101071",

language = "English",

volume = "61",

pages = "195--205",

journal = "Molecular Physics",

issn = "0026-8976",

publisher = "Taylor and Francis Ltd.",

number = "1",

}

TY - JOUR

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 - http://www.scopus.com/inward/record.url?scp=0000225348&partnerID=8YFLogxK

U2 - 10.1080/00268978700101071

DO - 10.1080/00268978700101071

M3 - Article

AN - SCOPUS:0000225348

SN - 0026-8976

VL - 61

SP - 195

EP - 205

JO - Molecular Physics

JF - Molecular Physics

IS - 1

ER -

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

Abstract

Access to Document

Other files and links

Fingerprint

Cite this