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The effects of nonlocal gradient corrections in density functional calculations of hydrocarbon radical hyperfine structures
Author(s) -
Eriksson Leif A.,
Malkin Vladimir G.,
Malkina Olga L.,
Salahub Dennis R.
Publication year - 1994
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.560520415
Subject(s) - hyperfine structure , isotropy , density functional theory , hyperfine coupling , chemistry , gaussian , coupling constant , atomic orbital , anisotropy , spin (aerodynamics) , ground state , spin density , molecular physics , atomic physics , computational chemistry , physics , quantum mechanics , condensed matter physics , thermodynamics , electron
Ground‐state equilibrium geometries and hyperfine structures of a number of organic neutral and charged radical compounds are computed using the linear combination of Gaussian‐type orbitals–density functional theory method. In addition to the local spin‐density approximation, we also use two different nonlocal (gradient corrected) schemes for the calculations of the exchange and correlation potentials. The different functional forms are found to generate slightly different total and unpaired spin‐density distributions in the molecules, and as a result, the computed isotropic hyperfine coupling constants vary markedly. The smallest variations are found for the hydrogens, where the results are generally in satisfactory agreement with experiment. For the carbon atoms, however, large differences in isotropic coupling constants are observed. The anisotropic hyperfine structures are generally very well described at all levels of theory. © John Wiley & Sons, Inc.