Relaxation and thermodynamic parameters of the theory of spin-wave damping in low-dimensional magnetic materials

Several basic parameters of the surface spectrum of a system are estimated with respect to the spin-spin interaction. An expression for the surface relaxation time and its numerical estimation are given. The dependence of the relaxation time on the geometric factor determined by the surface geometry only is presented. The conditions for the resonance absorption of spin-wave energy by the surface are considered. Certain expressions for the thermodynamic potentials taking the effect of surface resonance on the equilibrium properties of the system into account are given.     

A Model Calculation for the Isomerization and Decomposition of Chemisorbed HCN on the Si(100)-2×1 Surface

Ab initio molecular orbital and hybrid density functional theory calculations have been performed to study the adsorption, isomerization, and decomposition of HCN on Si(100)-2×1 using the Si₉H₁₂ cluster model of the surface. The results of our calculations indicate that the HCN can adsorb molecularly without a barrier onto the surface with both end-on (LM1) and side-on (LM2) positions. LM1 can isomerize to LM2 with a small barrier of 8 kcal/mol. The isomerization of LM2 by H-migration from C to the N atom, requires 76 kcal/mol activation energy (c.f. 47.5 kcal/mol in the gas phase) because of surface stabilization. Both HCN(a) and HNC(a) end-on adsorbates were found to dissociate readily, as concluded in our earlier experiment, to produce H and CN adspecies. The computed vibrational frequencies of HCN, CN, and also HCNH adspecies agree reasonably well with those observed experimentally. HCNH was found to be stable, with either the C or the N attaching to the surface.     

Ditantalum dinitrogen complex: reaction of H2 molecule with "end-on-bridged" [Ta(IV)]2(μ-η(1):η(1)-N2) and Bis(μ-nitrido) [Ta(V)]2(μ-N)2 complexes

To elucidate (i) the physicochemical properties of the {(η(5)-C(5)Me(5))[Ta(IV)](i-Pr)C(Me)N(i-Pr)}(2)(μ-η(1):η(1)-N(2)), I, [Ta(IV)](2)(μ-η(1):η(1)-N(2)), and {(η(5)-C(5)Me(5))[Ta(V)](i-Pr)C(Me)N(i-Pr)}(2)(μ-N)(2), II, [Ta(V)](2)(μ-N)(2), complexes; (ii) the mechanism of the I → II isomerization; and (iii) the reaction mechanism of these complexes with an H(2) molecule, we launched density functional (B3LYP) studies of model systems 1, 2, and 3 where the C(5)Me(5) and (i-Pr)C(Me)N(i-Pr) ligands of I (or II) were replaced by C(5)H(5) and HC(NCH(3))(2), respectively. These calculations show that the lower-lying electronic states of 1, [Ta(IV)](2)(μ-η(1):η(1)-N(2)), are nearly degenerate open-shell singlet and triplet states with two unpaired electrons located on the Ta centers. This finding is in reasonable agreement with experiments [J. Am Chem. Soc. 2007, 129, 9284-9285] showing easy accessibility of paramagnetic and diamagnetic states of I. The ground electronic state of the bis(μ-nitrido) complex 2, [Ta(V)](2)(μ-N)(2), is a closed-shell singlet state in agreement with the experimentally reported diamagnetic feature of II. The 1-to-2 rearrangement is a multistep and highly exothermic process. It occurs with a maximum of 28.7 kcal/mol free energy barrier required for the (μ-η(1):η(1)-N(2)) → (μ-η(2):η(2)-N(2)) transformation step. Reaction of 1 with H(2) leading to the 1,4-addition product 3 proceeds with a maximum of 24.2 kcal/mol free energy barrier associated by the (μ-η(1):η(1)-N(2)) → (μ-η(2):η(1)-N(2)) isomerization step. The overall reaction 1 + H(2) → 3 is exothermic by 20.0 kcal/mol. Thus, the addition of H(2) to 1 is kinetically and thermodynamically feasible and proceeds via the rate-determining (μ-η(1):η(1)-N(2)) → (μ-η(2):η(1)-N(2)) isomerization step. The bis(μ-nitrido) complex 2, [Ta(V)](2)(μ-N)(2), does not react with H(2) because of the large energy barrier (49.5 kcal/mol) and high endothermicity of the reaction. This conclusion is also in excellent agreement with the experimental observation [J. Am Chem. Soc. 2007, 129, 9284-9285].     

Insights into the mechanism of O₂ formation and release from the Mn₄O₄L₆ "cubane" cluster

To probe photoinduced water oxidation catalyzed by the Mn?O?L? cubane clusters, we have computationally studied the mechanism and controlling factors of the O? formation from the [Mn?O?L?] catalyst, 6. It was demonstrated that dissociation of an L = H?PO?? ligand from 6 facilitates the direct O-O bond formation that proceeds with a 28.3 (33.4) kcal/mol rate-determining energy barrier at the transition state TS1. This step (the O-O single bond formation) of the reaction is a two-electron oxidation/reduction process, during which two oxo ligands are transformed into to μ2:η2-O?2? unit, and two ("distal") Mn centers are reduced from the 4+ to the 3+ oxidation state. Next two-electron oxidation/reduction occurs by "dancing" of the resulted O?2? fragment between the Mn1 and Mn2/Mn(2')-centers, keeping its strong coordination to the Mn(1')-center. As a result of this four-electron oxidation/reduction process Mn centers of the Mn?-core of I transform from {Mn1(III)-Mn(1')(III)-Mn2(IV)-Mn(2')(IV)} to {Mn1(II)-Mn(1')(II)-Mn2(III)-Mn(2')(III)} in IV. In other words, upon O? formation in cationic complex [Mn?O?L?](+), I, all four Mn-centers are reduced by one electron each. The overall reaction I → TS1 → II → III → TS2 → IV → TS3 → V → VI + O? is found to be exothermic by 15.4 (10.5) kcal/mol. We analyze the lowest spin states and geometries of all reactants, intermediates, transition states, and products of the targeted reaction.     

Petroleum luminophores of pyrolytic origin and energy transfer between their components

Photoexcitation of luminophores prepared from heavy oil pyrolysis tar was studied, and properties of these compounds, determining the variation of the luminescence color and intensity depending on the solution concentration, were evaluated.     

Au, Ge, and AuGe nanoparticles fabricated by laser ablation

A eutectic AuGe target immersed in distilled water was ablated by pulsed ultraviolet laser light. The structure of the ablated material was investigated by high-resolution transmission electron microscopy (HRTEM). The images show formation of nanowire structures of AuGe up to 100 nm in length, with widths of 5–10 nm. These nanostructures have Ge content significantly lower than the target material. Electron diffraction demonstrates that they crystallize in the α-AuGe structure. For comparison, laser ablation of pure Au and pure Ge targets was also performed under the same conditions. HRTEM shows that Ge forms spherical nanoparticles with a characteristic size of ~30 nm. Au forms spherical nanoparticles with diameters of ~10 nm. Similar to AuGe, it also forms chainlike structures with substantially lower aspect ratio.     

Versatile and cooperative reactivity of a triruthenium polyhydride cluster. A computational study

The reaction of a trinuclear polyhydride complex Ru3H5(C5H5)3 with cyclopentadiene, C5H6, has been studied computationally. A mechanism for the experimentally observed selective C-C bond activation is proposed. All three Ru centers participate in various steps of the mechanism. The catalytic involvement of two cluster hydrides in the transformation of the C5Hn fragment is emphasized.