MO studies on the33S hyperfine splittings andg-factors of dithiin cation radicals
- 1 January 1976
- journal article
- research article
- Published by Taylor & Francis in Molecular Physics
- Vol. 31 (1) , 57-64
- https://doi.org/10.1080/00268977600100051
Abstract
The spin distribution and g-factors have been calculated for a number of dithiin cation radicals. The s-spin densities on sulphur calculated by the open-shell unrestricted INDO method both with and without annihilation of the quartet component have been correlated satisfactorily with the observed 33S hyperfine splittings. The g-factors calculated according to the Stone theory by an open-shell restricted version of the INDO method are found in good agreement with observation; their deviation from the free-spin comes from the large spin density localized on the sulphur atoms and the small excitation energy from the ‘NB’ sulphur orbitals to the odd MO. Comparative calculations with the sp and spd basis sets demonstrate the modest effect of the 3d(S) orbitals on the considered physical constants of the dithiin cations.Keywords
This publication has 16 references indexed in Scilit:
- Quantum Theoretical Considerations of the ortho:para Ratio for Proton Isotropic Hyperfine Coupling Constants in Benzyl RadicalThe Journal of Chemical Physics, 1971
- Applications of the INDO method to some radicals containing second row elementsTheoretical Chemistry Accounts, 1971
- Molecular orbital theory of the electronic structure of organic compounds. II. Spin densities in paramagnetic speciesJournal of the American Chemical Society, 1968
- Complete neglect of differential overlap calculations on second-row moleculesJournal of the American Chemical Society, 1968
- Approximate Self-Consistent Molecular-Orbital Theory. V. Intermediate Neglect of Differential OverlapThe Journal of Chemical Physics, 1967
- Molecular orbital theory of the electronic structure of organic compounds. I. Substituent effects and dipole momentsJournal of the American Chemical Society, 1967
- Gauge invariance of the g tensorProceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, 1963
- Single determinant wave functionsProceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, 1961
- The Electronic Spectra of Aromatic Molecules IV: Excited States of Odd Alternant Hydrocarbon Radicals and IonsProceedings of the Physical Society. Section A, 1955
- The crystal and molecular structure of 1,4-dithiadieneActa Crystallographica, 1954