title: First example of the correlated calculation of the one-bond tellurium-carbon spin-spin coupling constants: Relativistic effects, vibrational corrections, and solvent effects.
abstract: This work reports on the comprehensive calculation of the NMR one-bond spin-spin coupling constants (SSCCs) involving carbon and tellurium, (1) J((125) Te,(13) C), in four representative compounds: Te(CH3 )2 , Te(CF3 )2 , Te(CCH)2 , and tellurophene. A high-level computational treatment of (1) J((125) Te,(13) C) included calculations at the SOPPA level taking into account relativistic effects evaluated at the 4-component RPA and DFT levels of theory, vibrational corrections, and solvent effects. The consistency of different computational approaches including the level of theory of the geometry optimization of tellurium-containing compounds, basis sets, and methods used for obtainig spin-spin coupling values have also been discussed in view of reproducing the experimental values of the tellurium-carbon SSCCs. Relativistic corrections were found to play a major role in the calculation of (1) J((125) Te,(13) C) reaching as much as almost 50% of the total value of (1) J((125) Te,(13) C) while relativistic geometrical effects are of minor importance. The vibrational and solvent corrections account for accordingly about 3-6% and 0-4% of the total value. It is shown that taking into account relativistic corrections, vibrational corrections and solvent effects at the DFT level essentially improves the agreement of the non-relativistic theoretical SOPPA results with experiment. © 2016 Wiley Periodicals, Inc.
authors.affiliation: A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, Irkutsk, 664033, Russian Federation.
authors.forename: Irina L
authors.initials: IL
authors.lastname: Rusakova
authors.affiliation: A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, Irkutsk, 664033, Russian Federation.
authors.forename: Yury Yu
authors.initials: YY
authors.lastname: Rusakov
authors.affiliation: A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, Irkutsk, 664033, Russian Federation.
authors.forename: Leonid B
authors.initials: LB
authors.lastname: Krivdin
keywords: 125Te NMR; 4-component DFT; 4-component RPA; SOPPA; relativistic effects; tellurium-carbon spin-spin coupling constant