C_nP_4~4(n=1～7)团簇结构与能量的密度泛函研究

使用分子图形软件设计出多种CnP-4(n =1～ 7)的结构模型 ,并进行B3LYP密度泛函几何构型优化和振动频率计算 .最稳定的CP-4和C2 P-3 都是平面环状结构 .最稳定的CnP-4(n =3 ,5 ,7)结构在直碳链的一端连接 1个磷原子且另一端是P3 C的四元环的平面结构 .最稳定的CnP-4(n =4,6)结构在直碳链的一端连接 1个磷原子且另一端是P3 的三元环的锄状结构 .直碳链可与平面环的磷原子生成大π键 .大多数构型是由C2 ,C3 ,C4子结构以环状或链状方式组成的 .碳原子与磷原子以交替方式排列的结构数量少、能量高 .     

肾上腺素与二甲亚砜氢键作用的理论研究

采用PM 3半经验方法对肾上腺素和二甲亚砜与肾上腺素形成的 1∶1复合物的结构进行了几何优化 .在此基础上用密度泛函理论 (DFT)的B3LYP方法 ,分别在 6 31G、6 31G 、6 31+G 基组水平上进行了精确计算 ,并通过单点能计算考察了它们之间在形成各种复合物前后的能量和分子结构参数变化特点 .在各基组水平上所有物种的能量均进行零点振动能 (ZPVE)校正 .计算结果表明 ,二甲亚砜与肾上腺素能形成 6种稳定的复合物 ,在这些复合物中都具有较强的氢键作用 .计算结果能够解释有关实验现象     

Dynamics of Random One-Dimensional ±J Systems

Finite chains of a two-state random Potts spin model with periodic boundary conditions are studied within Glauber dynamics. The spin exchange is assumed random with frustration between ferro and antiferromagnetic values (±J). Time-dependent fluctuations are induced by periodic temperature oscillations. Master type differential equations for spin correlation functions are solved within linear response theory. The spectrum of relaxation times are calculated at different temperatures. The ±J Potts glass chains undergo a zero temperature phase transition. The barriers against inversion of the spin chain take only two values; 0 and 2|J|. The temperature behaviour of specific heat is characterized by rounded peaks. The frequency dependence displays two plateaus for the real part of specific heat and two corresponding peaks for the imaginary part. The dynamic specific heat is not affected by the longest relaxing mode like susceptibility. The time separation of the modes is demonstrated by the Cole-Cole plots.     

Adsorption of argon and nitrogen in cylindrical pores of MCM-41 materials: application of density functional theory

Adsorption of argon and nitrogen at their respective boiling points in cylindrical pores of MCM-41 type silica-like adsorbents is studied by means of a non-local density functional theory (NLDFT), which is modified to deal with amorphous solids. By matching the theoretical results of the pore filling pressure versus pore diameter against the experimental data, we arrive at a conclusion that the adsorption branch (rather than desorption) corresponds to the true thermodynamic equilibrium. If this is accepted, we derive the optimal values for the solid-fluid molecular parameters for the system amorphous silica-Ar and amorphous silica-N₂, and at the same time we could derive reliably the specific surface area of non-porous and mesoporous silica-like adsorbents, without a recourse to the BET method. This method is then logically extended to describe the local adsorption isotherms of argon and nitrogen in silica-like pores, which are then used as the bases (kernel) to determine the pore size distribution. We test this with a number of adsorption isotherms on the MCM-41 samples, and the results are quite realistic and in excellent agreement with the XRD results, justifying the approach adopted in this paper.     

Shifting the Superparamagnetic Limit of Nanosized Copper Iron Spinel

In this paper we analyze trend of EFG values measured at Cd impurity in a group of semiconducting delafossites with chemical formula CuBO₂ (B = Al, Fe, Cr, Nd). We conclude that this trend reveals one of the most subtle details in electronic spectrum of the compounds: if impurity states are formed within or out of the band gap. In CuAlO₂ and CuFeO₂ the Cd EFG exhibits larger value than in CuCrO₂ and CuNdO₂, when Cd substitutes the Cu atom. This occurs because in the first two compounds the Cd forms shallow band within the gap, and in the second two compounds does not. When Cd occupies the B position it exhibits almost the same EFG in all delafossites. In this case, Cd does not form its states within the gap in none of the compounds. To arrive to these conclusions we analyzed and calculated various systems (Cd-doped CuAlO₂ and CuCrO₂ compounds, fictitious molecules), using the FP-LAPW method.     

Quantum Phase Transition in Quasi-two-dimensional Heisenberg Antiferromagnet with Single-Ion Anisotropy

In the present paper, we investigate the quantum phase transition in a spatially anisotropic antiferrornagnetic Heisenberg model of S =1 with single-ion energy anisotropy. By using the Schwinger boson representation, we calculate the Gaussian correction to the critical value J⊥^c caused by quantum spin fluctuations. We find that, for the positive single-ion energy, a nonzero value of J⊥^c is always needed to stabilize the antiferromagnetic long-range order in this model. It resolves a difference among literature and shows clearly that the effect of quantum fluctuations may qualitatively change a result obtained by the mean-field theories on lower-dimensional systems.     

A first-principles study of surface and subsurface H on and in Ni(1 1 1): diffusional properties and coverage-dependent behavior

Periodic, self-consistent, density functional theory (GGA-PW91) calculations are performed for both surface and subsurface atomic hydrogen on and in Ni(1 1 1). At a low coverage (θ=0.25 ML), the binding energies (BEs) of a hydrogen atom in surface fcc, subsurface octahedral (first layer), and subsurface octahedral (second layer) sites are −2.89, −2.18, and −2.11 eV, respectively. The activation energy barriers for hydrogen diffusion from the surface to the first subsurface layer and from the first to the second subsurface layer are estimated to be 0.88 and 0.52 eV, respectively. In the entire coverage range studied, hydrogen occupies surface fcc and hcp sites and subsurface octahedral sites. In addition, the magnitude of the BE per hydrogen atom and the magnetization of the nickel slabs both decrease as hydrogen coverage increases. Vibrational frequencies of hydrogen at various surface and subsurface sites are calculated and are in reasonable agreement with experimental data. A phase stability calculation with a 2 × 2 surface unit cell shows that a p(2 × 2)-2H overlayer structure (θ=0.5 ML) and a p(1 × 1)-1H structure (θ=1.0 ML) are stable at low hydrogen pressures, in agreement with numerous experimental results. A very large increase in pressure is required to populate subsurface sites. After such an increase occurs, the first subsurface layer is filled completely.     

B-Theory of Runge-Kutta methods for stiff volterra functional differential equations

B-stability andB-convergence theories of Runge-Kutta methods for nonlinear stiff Volterra functional differential equations (VFDEs) are established which provide unified theoretical foundation for the study of Runge-Kutta methods when applied to nonlinear stiff initial value problems (IVPs) in ordinary differential equations (ODEs), delay differential equations (DDEs), integro-differential equations (IDEs) and VFDEs of other type which appear in practice.     

Quantum-Chemical Study of the Profiles of Reactions that Form Pyrrole Anion N-Adducts with CS<Subscript>2</Subscript> and CO<Subscript>2</Subscript>

The profiles of reactions leading to pyrrole anion N-adducts with CO₂ and CS₂ have been studied by the ab initio (RHF/6-31+G*, MP2/6-31+G*) and density functional (B3LYP/6-31+G*) methods. Addition of the pyrrole anion to the carbon disulfide molecule is accompanied by the appearance of a minimum corresponding to a pre-reaction complex. The transformation of the complex to the N-pyrrolyldithiocarboxylate anion occurs via a low activation barrier, which is due to repolarization of the C=S bonds. The profile of the reaction leading to the pyrrole anion N-adduct with CO₂ does not contain any intermediate stationary points throughout the whole route from reagents to products.Original Russian Text Copyright © 2004 by V. B. Kobychev, N. M. Vitkovskaya, I. L. Zaitseva, and B. A. Trofimov__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 6, pp. 990–993, November–December, 2004.