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Full four‐component relativistic calculations of the one‐bond 77 Se– 13 C spin‐spin coupling constants in the series of selenium heterocycles and their parent open‐chain selenides
Author(s) -
Rusakov Yury Yu.,
Rusakova Irina L.,
Krivdin Leonid B.
Publication year - 2014
Publication title -
magnetic resonance in chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.483
H-Index - 72
eISSN - 1097-458X
pISSN - 0749-1581
DOI - 10.1002/mrc.4053
Subject(s) - chemistry , relativistic quantum chemistry , coupling constant , scalar (mathematics) , spin (aerodynamics) , selenium , polarizability , atomic physics , computational chemistry , molecule , quantum mechanics , physics , thermodynamics , geometry , mathematics , organic chemistry
Four‐component relativistic calculations of 77 Se– 13 C spin–spin coupling constants have been performed in the series of selenium heterocycles and their parent open‐chain selenides. It has been found that relativistic effects play an essential role in the selenium–carbon coupling mechanism and could result in a contribution of as much as 15–25% of the total values of the one‐bond selenium–carbon spin‐spin coupling constants. In the overall contribution of the relativistic effects to the total values of 1 J (Se,C), the scalar relativistic corrections (negative in sign) by far dominate over the spin‐orbit ones (positive in sign), the latter being of less than 5%, as compared to the former ( ca 20%). A combination of nonrelativistic second‐order polarization propagator approach (CC2) with the four‐component relativistic density functional theory scheme is recommended as a versatile tool for the calculation of 1 J (Se,C). Solvent effects in the values of 1 J (Se,C) calculated within the polarizable continuum model for the solvents with different dielectric constants ( ε 2.2–78.4) are next to negligible decreasing negative 1 J (Se,C) in absolute value by only about 1 Hz. The use of the locally dense basis set approach applied herewith for the calculation of 77 Se– 13 C spin‐spin coupling constants is fully justified resulting in a dramatic decrease in computational cost with only 0.1–0.2‐Hz loss of accuracy. Copyright © 2014 John Wiley & Sons, Ltd.