Evaluation of a new procedure for quantum-chemical estimates of constants of isotropic hyperfine coupling with protons in free radicals |
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| Authors: | N D Chuvylkin A M Tokmachev |
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| Institution: | (1) N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 117913 Moscow, Russian Federation;(2) Department of Chemistry, M. V. Lomonosov Moscow State University, Leninskie Gory, 119899 Moscow, Russian Federation |
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| Abstract: | A new procedure for quantum-chemical estimates of the constants of isotropic hyperfine coupling (IHFC) with protons using the orbital spin populations calculated in the basis set of symmetrically orthogonalized (according to Löwdin) atomic orbitals is tested taking 16 well-studied simplest π-electron and σ-electron radicals as examples. The most probable reasons for and possible ways of correcting large deviations of calculated IHFC constants from experimental values are considered. The efficiency of the semiempirical MNDORU scheme, which makes it possible to consistently estimate the delocalization and spin-polarization contributions to the constants of IHFC with protons in free radicals, is demonstrated. |
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| Keywords: | ESR spectroscopy free radicals constants of isotropic hyperfine coupling with protons quantum-chemical estimates symmetrically orthogonalized basis set of atomic orbitals |
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