The Role of Radical Bridges in Polynuclear Single-Molecule Magnets

Employing radical bridges between anisotropic metal ions has been a viable route to achieve high-performance single-molecule magnets (SMMs). While the bridges have been mainly considered for their ability to promote exchange interactions, the crystal-field effect arising from them has not been taken into account explicitly. This lack of consideration may distort the understanding and limit the development of the entire family. To shed light on this aspect, herein we report a theoretical investigation of a series of N -radical-bridged diterbium complexes. It is found that while promoting strong exchange coupling between the terbium ions, the N -radical induces a crystal field that interferes destructively with that of the outer ligands, and thus reduces the overall SMM behavior. Based on the theoretical results, we conclude that the SMM behavior in this series could be further maximized if the crystal field of the outer ligands is designed to be collinear with that of the radical bridge. This conclusion can be generalized to all exchange-coupled SMMs.     

The Squeezing Effect in a Mesoscopic RLC Circuit

Using the path integral method we derive quantum wave function and quantum fluctuations of charge andcurrent in the mesoscopic RLC circuit. We find that the quantum fluctuation of charge decreases with time, oppositely,the quantum fluctuation of current increases with time monotonously. Therefore there is a squeezing effect in the circuit.If some more charge devices are used in the mesoscopic-damped circuit, the quantum noise can be reduced. We also findthat uncertainty relation of charge and current periodically varies with the period π/2 in the under-damped case.     

Effect of the Electron-LO-Phonon Coupling on an Exciton Quantum Dot

The influence of the electron-LO-phonon coupling on energy spectrum of the low-lying states ofan exciton inparabolic quantum dots is investigated as a function of dot size. Calculations are made by using the method of few-bodyphysics within the effective-mass approximation. A considerable decrease of the energy in the stronger confinement rangeis found for the low-lying states of an exciton in quantum dots, which results from the confinement of electron-phononcoupling.     

An implicit characteristic-flux-averaging method for the euler equations for real gases

A formulation of an implicit characteristic-flux-averaging method for the unsteady Euler equations with real gas effects is presented. Incorporation of a real gas into a general equation of state is achieved by considering the pressure as a function of density and specific internal energy. The Ricmann solver as well as the flux-split algorithm are modified by introducing the pressure derivatives with respect to density and internal energy. Expressions for calculating the values of the flow variables for a real gas at the cell faces are derived. The Jacobian matrices and the eigenvectors are defined for a general equation of state. The solution of the system of equations is obtained by using a mesh-sequencing method for acceleration of the convergence. Finally, a test case for a simple form of equation of state displays the differences from the corresponding solution for an ideal gas.     

Monte Carlo Hamiltonian: Linear Potentials

We further study the validity of the Monte Carlo Hamiltonian method. The advantage of the method,in comparison with the standard Monte Carlo Lagrangian approach, is its capability to study the excited states. Weconsider two quantum mechanical models: a symmetric one V(x) = |x|/2; and an asymmetric one V(x) = ∞, forx ＜ 0 and V(x) = x, for x ≥ 0. The results for the spectrum, wave functions and thermodynamical observables are inagreement with the analytical or Runge-Kutta calculations.     

氢原子的固有电偶极矩

用经典力学和双波量子力学计算了氢原子的固有电偶极矩。双波量子理论算得的结果在经典极限下与经典力学的结果一致。普通量子力学对氢原子Stark效应中表现出来的电偶极矩难以做出很好的解释，因为一个波函数描述的是系综而不是单个粒子。经典力学和双波量子力学可描述单个粒子的行为，对永久电偶极矩的计算和解释显得自然而合理。     

Deactivation reactions in the modeled 2,2,6,6‐tetramethyl‐1‐piperidinyloxy‐mediated free‐radical polymerization of styrene: A comparative study with the 2,2,6,6‐tetramethyl‐1‐piperidinyloxy/acrylonitrile system

The competitiveness of the combination and disproportionation reactions between a 1‐phenylpropyl radical, standing for a growing polystyryl macroradical, and a 2,2,6,6‐tetramethyl‐1‐piperidinyloxy (TEMPO) radical in the nitroxide‐mediated free‐radical polymerization of styrene was quantitatively evaluated by the study of the transition geometry and the potential energy profiles for the competing reactions with the use of quantum‐mechanical calculations at the density functional theory (DFT) UB3‐LYP/6‐311+G(3df, 2p)//(unrestricted) Austin Model 1 level of theory. The search for transition geometries resulted in six and two transition structures for the radical combination and disproportionation reactions, respectively. The former transition structures, mainly differing in the out‐of‐plane angle of the N? O bond in the transition structure TEMPO molecule, were correlated with the activation energy, which was determined to be in the range of 8.4–19.4 kcal mol^?1 from a single‐point calculation at the DFT UB3‐LYP/6‐311+G(3df, 2p)//unrestricted Austin Model 1 level. The calculated activation energy for the disproportionation reaction was less favorable by a value of more than 30 kcal mol^?1 in comparison with that for the combination reaction. The approximate barrier difference for the TEMPO addition and disproportionation reaction was slightly smaller for the styrene polymerization system than for the acrylonitrile polymerization system, thus indicating that a β‐proton abstraction through a TEMPO radical from the polymer backbone could diminish control over the radical polymerization of styrene with the nitroxide even more than in the latter system. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 232–241, 2007     

Geometry and electronic structure of a heterometallic cluster Mo<Subscript>2</Subscript>Mg<Subscript>2</Subscript> in different oxidation states of Mo: a DFT study

Reduction of tetranuclear heterometallic complex Mo₂Mg₂ was simulated using the B3LYP and PBE density functional methods. The results of geometry calculations of the initial complex [Mo^VIO₂Mg(MeOH)₂(OMe)₄]₂ and a partially reduced Mo^V complex are in good agreement with experimental data. The reduced Mo^III complex is characterized by a decrease in the binding energy of aqua ligands. Structural rearrangement of the complex with release of a coordination position at the Mo atoms requires small energy expenditure. One can assume that the reduction of the polynuclear complex causes overcrowding of its coordination sphere, which favors formation of dinitrogen complexes. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 441–457, March, 2008.     

A method and program for mass quantum chemical calculations of protein—ligand docking complexes

A new fast computational method for mass calculations of docking complexes by the AM1/PM3 semiempirical methods is proposed. The computation time is shortened by at least an order of magnitude compared to alternative schemes of quantum chemical calculations. The root-mean-square deviation of the AM1 calculated energies of formation of complexes from the results obtained by conventional diagonalization procedure is at most 0.4 kcal mol⁻¹. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 418–420, February, 2008.