Publication record
Relativistic spin-orbit coupling effects on secondary isotope
shifts of 13C nuclear shielding in CX2 (X = O, S, Se, Te)
| Title | Relativistic spin-orbit coupling effects on secondary isotope
shifts of 13C nuclear shielding in CX2 (X = O, S, Se, Te) |
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| Authors | P. Lantto, J. Vaara, Anu Kantola, Ville-Veikko Telkki, B. Schimmelpfennig, K. Ruud and J. Jokisaari |
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| Citation | JACS 124(11); 2762-2771 |
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| Doi: | |
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| Year | 2002 |
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| Field | Spin Chemistry, Molecular Magnetism and Relativity |
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| Section | Molecular magnetism, NMR and ESR parameters |
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| Sub-section | General magnetism |
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| Keywords | NMR, SO-coupling |
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| Abstract | Rovibrational corrections, temperature dependence, and secondary
isotope shifts of the 13C nuclear shielding in CX2 (X = O, S,
Se, Te) are calculated taking into account the relativistic spin-orbit
(SO) interaction. The SO effect is considered for the first time for
the secondary isotope shifts. The nuclear shielding hypersurface in
terms of nuclear displacements is calculated using a
density-functional theory method.
%, including both second- and
%third-order SO contributions.
\em Ab initio\/ multiconfiguration self-consistent field
calculations are done at the equilibrium geometry for
comparison. 13C NMR measurements are carried out for CS2. The
calculated results are compared with both present and earlier
experimental data on CO2, CS2, and CSe2. The heavy-atom SO
effects on the rovibrational corrections of 13C shielding are
shown to be very significant. For CSe2 and CTe2, reliable
prediction of secondary isotope effects and their temperature
dependence necessitates including the SO corrections. In particular,
earlier discrepancies of theory and experiment for CSe2 are fully
resolved by taking SO interaction into account. |
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