ESR, spectroscopic, and quantum-chemical studies on the electronic structures of complexes formed by Cu(I) with radicals (in Russian)
The optical and ESR spectra have been examined for complexes of Cu(I) with various radicals, which contain various numbers of Cl/sup -/ ions in the central-atom coordination sphere. The spin-Hamiltonian parameters have been determined for all these radical complexes, and the observed ESR spectra have been compared with those calculated with allowance for second-order effects. The observed values for the isotropic and anisotropic components of the HFI constant from the central ion have been used to estimate the contributions from the 4s and 3d/sup 2//sub z/ orbitals of the copper ion to the unpaired-electron MO. Quantum-chemical calculations have been performed by the INDO method on the electronic structures and geometries of complexes formed by CH/sub 2/OH with Cu(I) for various Cl/sup -/ contents in the coordination sphere. The radical is coordinated by the ..pi.. orbital on the carbon atom, and the stabilities of the radical complexes decrease as the number of Cl/sup -/ ions in the coordination sphere increases. A geometry close to planar for the CuCl/sub 4//sup 3 -/ fragment in a complex containing four Cl/sup -/ ions.
- Research Organization:
- Institute of Chemical Kinetics and Combustion, Novosibirsk, USSR
- OSTI ID:
- 6191565
- Journal Information:
- Theor. Exp. Chem. (Engl. Transl.); (United States), Vol. 22:1; Other Information: Translated from Teor. Eksp. Khim.; 22: No. 1, 32-38(Jan-Feb 1986)
- Country of Publication:
- United States
- Language:
- Russian
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
74 ATOMIC AND MOLECULAR PHYSICS
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
COPPER COMPLEXES
ATOMIC MODELS
ELECTRON SPIN RESONANCE
ELECTRONIC STRUCTURE
PHOTOLYSIS
RADIOLYSIS
RADICALS
COMPLEXOMETRY
CHARGE DENSITY
ELECTRON TRANSFER
EXCITED STATES
GAMMA RADIATION
HAMILTONIANS
HARTREE-FOCK METHOD
HYPERFINE STRUCTURE
IRRADIATION
MOLECULAR ORBITAL METHOD
QUANTUM MECHANICS
SOLVATED ELECTRONS
SPIN
ANGULAR MOMENTUM
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
DECOMPOSITION
ELECTROMAGNETIC RADIATION
ELECTRONS
ELEMENTARY PARTICLES
ENERGY LEVELS
FERMIONS
IONIZING RADIATIONS
LEPTONS
MAGNETIC RESONANCE
MATHEMATICAL MODELS
MATHEMATICAL OPERATORS
MECHANICS
PARTICLE PROPERTIES
PHOTOCHEMICAL REACTIONS
QUANTUM OPERATORS
RADIATION CHEMISTRY
RADIATION EFFECTS
RADIATIONS
RESONANCE
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties
640302 - Atomic
Molecular & Chemical Physics- Atomic & Molecular Properties & Theory
400600 - Radiation Chemistry