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Long‐range relativistic heavy atom effect on 1 H NMR chemical shifts of selenium‐ and tellurium‐containing compounds
Author(s) -
Rusakov Yuriy Yu.,
Rusakova Irina L.
Publication year - 2019
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.25809
Subject(s) - chemical shift , selenium , chemistry , tellurium , relativistic quantum chemistry , proton , atom (system on chip) , range (aeronautics) , atomic physics , computational chemistry , physics , inorganic chemistry , nuclear physics , materials science , organic chemistry , computer science , composite material , embedded system
Abstract Previously unknown manifestation of heavy atom effect on the NMR chemical shifts of β‐ and γ‐protons initiated by the relativistic effects of the tellurium and selenium atoms has been investigated in the representative series of selenium‐ and tellurium‐containing compounds. To approve the four‐component density functional approach to be the appropriate tool for the investigation of the heavy atom on light atom effect (HALA), the benchmark calculations of the proton chemical shifts have been performed at the CCSD level using comprehensively chosen locally dense basis set with taking into account solvent, vibrational, and relativistic corrections. A good agreement with the experimental data was achieved. The magnitudes of the relativistic HALA corrections to β‐ and γ‐proton chemical shifts were found to vary in a wide range, namely from −3.08 ppm for the γ‐proton of methyltelluraldehyde to 14.51 ppm for β‐proton in benzotelluraldehyde.