Combined charge and spin density experimental study of the yttrium(III) semiquinonato complex Y(HBPz3)2(DTBSQ) and DFT calculations

High-resolution X-ray diffraction and polarized neutron diffraction experiments have been performed on the Y-semiquinonate complex, Y(HBPz3)2(DTBSQ), in order to determine the charge and spin densities in the paramagnetic ground state, S = (1/2). The aim of these combined studies is to bring new insights to the antiferromagnetic coupling mechanism between the semiquinonate radical and the rare earth ion in the isomorphous Gd(HBPz3)2(DTBSQ) complex. The experimental charge density at 106 K yields detailed information about the bonding between the Y3+ ion and the semiquinonate ligand; the topological charge of the yttrium atom indicates a transfer of about 1.5 electrons from the radical toward the Y3+ ion in the complex, in agreement with DFT calculations. The electron density deformation map reveals well-resolved oxygen lone pairs with one lobe polarized toward the yttrium atom. The determination of the induced spin density at 1.9 K under an applied magnetic field of 9.5 T permits the visualization of the delocalized magnetic orbital of the radical throughout the entire molecule. The spin is mainly distributed on the oxygen atoms [O1 (0.12(1) mu B), O2(0.11(1) mu B)] and the carbon atoms [C21 (0.24(1) mu B), C22(0.20(1) mu B), C24(0.16(1) mu B), C25(0.12(1) mu B)] of the carbonyl ring. A significant spin delocalization on the yttrium site of 0.08(2) mu B is observed, proving that a direct overlap with the radical magnetic orbital can occur at the rare earth site and lead to antiferromagnetic coupling. The DFT calculations are in good quantitative agreement with the experimental charge density results, but they underestimate the spin delocalization of the oxygen toward the yttrium and the carbon atoms of the carbonyl ring.     

The prism algorithm for two-electron integrals

A new approach to the evaluation of two-electron repulsion integrals over contracted Gaussian basis functions is developed. The new scheme encompasses 20 distinct, but interrelated, paths from simple shell-quartet parameters to the target integrals, and, for any given integral class, the path requiring the fewest floating-point operations (FLOPS ) is that used. Both theoretical (FLOP counting) and practical (CPU timing) measures indicate that the method represents a substantial improvement over the HGP algorithm.     

A sum rule approach to collective spin modes in paramagnetic clusters,cavities and shells

We study spin collective modes in paramagnetic systems using a sum rule approach. We give a simple and analytical expression for the static magnetic polarizability of finite size systems in terms of their radii and of the magnetic susceptibility of a uniform system. A systematics for the mean excitation energy of spin modes in clusters and shells is given. In metal spheres, the hydrodynamical model is solved and compared with the sum rule approach. An estimate for the mean excitation energy of the spin dipole collective state in fullerene is given.     

Role of tetraethoxysilane hydrolysis and polycondensation catalysts in synthesis of wide-pore silica gels

A study has been made of the effect of combining tetraethoxysilane hydrolysis and polycondensation catalysts operating by different mechanisms on the texture parameters of synthesized silica gels. The effect of hydrothermal treatment of a fluorine-containing silica hydrogel on the thermal stability of the xerogel texture was demonstrated.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 30, No. 2, pp. 95–98, March–April, 1994.     

A Possibility of Improving Lead Dioxide Electrode of Lead Battery

The influence exerted by a reinforcing additive, an aqueous suspension of 4D fluoroplastic (Teflon), on the structural, physicochemical, and service characteristics of the positive electrode of the lead battery was studied. A paste with polymer and carbon additives, extending the service life of the lead dioxide electrode, was developed for industrial use.     

Photosensitivity of holographic recording media based on films of polymer compositions with cadmium sulfide nanoparticles

The effect of doping with CdS nanoparticles of recording medium films for the thermoplastic holographic recording process, which are based on photosemiconductors (oligomers and cooligomers of glycidylcarbazole) and a dielectric (a styrene copolymer with octyl methacrylate) containing a photoconductivity sensitizer, on their photosensitivity was studied. The enhancement of photosensitivity of films by doping with nanoparticles is associated with the appearance of an additional channel for transport of electrons generated from sensitizer molecules. A difference in informational properties between the oligomer and the polymer films was revealed.