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Relativistic effects in the one‐bond spin–spin coupling constants involving selenium
Author(s) -
Rusakova Irina L.,
Rusakov Yury Yu.,
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.4112
Subject(s) - chemistry , relativistic quantum chemistry , dihedral angle , scalar (mathematics) , spin (aerodynamics) , selenium , coupling constant , density functional theory , atomic physics , computational chemistry , quantum mechanics , thermodynamics , physics , molecule , geometry , organic chemistry , hydrogen bond , mathematics
One‐bond spin–spin coupling constants involving selenium of seven different types, 1 J(Se,X) , X = 1 H, 13 C, 15 N, 19 F, 29 Si, 31 P, and 77 Se, were calculated in the series of 14 representative compounds at the SOPPA(CCSD) level taking into account relativistic corrections evaluated both at the RPA and DFT levels of theory in comparison with experiment. Relativistic corrections were found to play a major role in the calculation of 1 J(Se,X) reaching as much as almost 170% of the total value of 1 J(Se,Se) and up to 60–70% for the rest of 1 J(Se,X) . Scalar relativistic effects (Darwin and mass‐velocity corrections) by far dominate over spin–orbit coupling in the total relativistic effects for all 1 J(Se,X) . Taking into account relativistic corrections at both random phase approximation and density functional theory levels essentially improves the agreement of theoretical results with experiment. The most ‘relativistic’ 1 J(Se,Se) demonstrates a marked Karplus‐type dihedral angle dependence with respect to the mutual orientation of the selenium lone pairs providing a powerful tool for stereochemical analysis of selenoorganic compounds. Copyright © 2014 John Wiley & Sons, Ltd.