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11.
A combined calculation method of weak exchange interactions in short biradicals was developed. The combined method includes two stages. The quantum chemical calculations of the high level of the biradical structure and molecular orbitals and binding energies of unpaired electrons are performed at the first stage. Information obtained at the first stage is used further to calculate the exchange interaction between unpaired electrons within the direct exchange model using the asymptotic method. This allows one to estimate the exchange interaction and to determine the dependence of this interaction on the distance between the paramagnetic centers and on their relative orientation. The method developed was used to calculate the exchange interaction in the short nitroxyl biradical containing no conjugate rings between the paramagnetic NO groups. The geometry and electronic structure of the biradical were calculated within the unrestricted DFT method (B3LYP/cc-pvdz) using the ORCA program package. 相似文献
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D. K. Danovich B. N. Plakhutin V. K. Voronov 《Theoretical and Experimental Chemistry》1990,26(2):208-212
The INDO UHF method has been applied to the complexes CuCl2L4 (L=1-vinylimidazole, NH3) to calculate the isotropic (Fermi contact) paramagnetic shifts in the1H and13C NMR spectra. The structure of the complexes in solution was elucidated by comparison with experimental data, and some methodological aspects of the calculation have been considered.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 26, No. 2, pp. 225–229, March–April, 1990. 相似文献
14.
G. T. Klimko M. M. Mestechkin B. N. Plakhutin G. M. Zhidomirov R. A. Evarestov 《International journal of quantum chemistry》1990,37(1):35-50
Different methods of averaging of energy over the states of electronic configurations γN (nγ = 1, 2, 3 and N = 1, 2, …, 2nγ ? 1) leading to Roothaan' energy expression are considered. The consequent values of vector coupling coefficients (VCC ) in energy functionals for various states as well as for average values of energy are presented. It is shown also that in molecular systems of cubic and tetragonal symmetry having electronic configurations tN (N = 2–4) and e2 there exist states for which VCC are dependent on the choice of basis set of degenerate open-shell molecular orbitals. The origin of such “non-Roothaan” terms and peculiarities of its calculation by the restricted Hartree–Fock method are discussed. 相似文献
15.
Group-theoretical and quantum-chemical investigations of the spectrum of low-lying excited states have been performed by the ROHF and FCI-RAS (Full CI in Restricted Active Space) methods for 3d metal endofullerenes (MEFs) M@C60 (M =Mn, Cr, and Fe) in different charged states. The major purpose of this study is quantum-chemical verification of the anomalous (“non-Bethe’s”) character of splitting of the d N atomic states in an electrostatic field with icosahedral symmetry, predicted previously within the theory of integral invariants theory. The interrelation between the integral invariants theory and the quantumchemical methods applied in this work is considered in detail. Our calculations suggest that the d N atomic states in the icosahedral field generated by fullerene C60 (I h ) on a metal atom (ion) remain non-split for different charged states of the metal and C60. Reasons for this phenomenon and other possible approaches to verification of the prediction are discussed. It is demonstrated that the d N states of the encapsulated metal are split in icosahedral 3d MEFs only under very strong compression of these structures. 相似文献
16.
B. N. Plakhutin 《Journal of Structural Chemistry》1998,39(1):1-13
A numerical procedure for expanding electron repulsion integrals 〈mm|nn〉 on degenerate molecular orbitals of γ symmetry (γ=e, t, g, h) into integral invariants (reduced matrix elements) Hk(γ, γ) is suggested. The latter are analogous in their sense to Slater-Condon parameters Fk(l, l) for atoms with an electronic configuration lN. The method is applicable to nonlinear molecules of arbitrary symmetries, including “not readily reducible” groups.
G. K. Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences. Translated fromZhurnal Strukturnoi Khimii, Vol. 39, No. 1, pp. 3–17, January–February, 1998.
This work was supported by RFFR grants No. 96-03-01167 and 96-03-34035. 相似文献
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We have investigated the superconducting properties of the Bi1.7 Pb0.3Sr2Ca2−xCe
x
Cu3O10+δ system with x=0.00, 0.02, 0.04, 0.08 and 0.1 by X-ray diffraction and magnetic susceptibility. The substitution of Ce for Ca has been found
to drastically change the superconducting properties of the system. X-ray diffraction studies on these compounds indicate
decrease in the c-parameter with increased substitution of Ce at Ca site and volume fraction of high T
c (2 : 2 : 2 : 3) phase decreases and low T
c phase increases. The magnetic susceptibility of this compound shows that the diamagnetic on set superconducting transition
temperature (onset) varies from 109 K to 51 K for x=0.00, 0.02, 0.04, 0.08 and 0.1. These results suggest the possible existence of Ce in a tetravalent state rather than a trivalent
state in this system; that is, Ca2+ → Ce4+ replacement changes the hole carrier concentration. Hole filling is the cause of lowering T
c of the system. 相似文献
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We have deposited relatively thick (∼60 nm) Ge layers on Br-passivated Si(111) substrates by thermal evaporation under high
vacuum conditions at room temperature. Ge has grown in a layer-plus-island mode although it is different from the Stranski-Krastanov
growth mode observed in epitaxial growth. Both the islands and the layer are nanocrystalline. This appears to be a consequence
of reduction of surface free energy of the Si(111) substrate by Br-passivation. The size distribution of the Ge nanoislands
has been determined. The Br-Si(111) substrates were prepared by a liquid treatment, which may not produce exactly reproducible
surfaces. Nevertheless, some basic features of the nanostructural island growth are reasonably reproducible, while there are
variations in the details of the island size distribution. 相似文献