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First example of the correlated calculation of the one‐bond tellurium–carbon spin–spin coupling constants: Relativistic effects, vibrational corrections, and solvent effects
Author(s) -
Rusakova Irina L.,
Rusakov Yury Yu.,
Krivdin Leonid B.
Publication year - 2016
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.24345
Subject(s) - tellurium , relativistic quantum chemistry , chemistry , spin (aerodynamics) , coupling constant , solvent effects , coupling (piping) , bond length , consistency (knowledge bases) , computational chemistry , solvent , molecule , atomic physics , physics , thermodynamics , quantum mechanics , materials science , organic chemistry , mathematics , geometry , metallurgy
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(CH 3 ) 2 , Te(CF 3 ) 2 , Te(CCH) 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.