Calculations of molecular multipole electric moments of a series of exo-insaturated four-membered heterocycles,Y = CCH2CH2X

The influence of ring puckering angle on the multipole moments of sixteen four-membered heterocycles (1-16) was theoretically estimated using MP2 and different DFTs in combination with the 6-31+G(d,p) basis set. To obtain an accurate evaluation, CCSD/cc-pVDZ level and, the MP2 and PBE1PBE methods in combination with the aug-cc-pVDZ and aug-cc-pVTZ basis sets were performed on the planar geometries of 1-16. In general, the DFT and MP2 approaches provided an identical dependence of the electrical properties with the puckering angle for 1-16. Quantitatively, the quality of the level of theory and basis sets affects significant the predictions of the multipole moments, in particular for the heterocycles containing C=O and C=S bonds. Convergence basis sets within the MP2 and PBE1PBE approximations are reached in the dipole moment calculations when the aug-cc-pVTZ basis set is used, while the quadrupole and octupole moment computations require a larger basis set than aug-cc-pVTZ. On the other hand, the multipole moments showed a strong dependence with the molecular geometry and the nature of the carbon-heteroatom bonds. Specifically, the C-X bond determines the behavior of the μ(?), θ(?) and ?(?) functions, while the C=Y bond plays an important role in the magnitude of the studied properties.     

Magnetic moment of phonons in graphene induced by a magnetic field

A magnetic field not only changes the electronic structure in graphene but also affects the phonon excitations via the electron-phonon interaction and even enables the phonons to generate magnetism. In this paper, we evaluate the magnetic moment of phonons in graphene using a generating-functional technique. The calculation results indicate that the phonon magnetic moment exists only in a weak magnetic field. The step-like change of the magnetic moment with the magnetic field reflects a macroscopic quantum effect.     

On a new class of multiplicative pseudo-random number generators

In the computing literature, there are few detailed analytical studies of the global statistical characteristics of a class of multiplicative pseudo-random number generators.We comment briefly on normal numbers and study analytically the approximately uniform discrete distribution or (j,)-normality in the sense of Besicovitch for complete periods of fractional parts {x _{0 1} ⁱ /p} on [0, 1] fori=0, 1,..., (p–1)p^–1–1, i.e. in current terminology, generators given byx _{n+1 1} x _n mod p wheren=0, 1,..., (p–1)p ^–1–1,p is any odd prime, (x ₀,p)=1, ₁ is a primitive root modp ², and 1 is any positive integer.We derive the expectationsE(X, ),E(X ², ),E(X _nX_n+k); the varianceV(X, ), and the serial correlation coefficient k. By means of Dedekind sums and some results of H. Rademacher, we investigate the asymptotic properties of k for various lagsk and integers 1 and give numerical illustrations. For the frequently used case =1, we find comparable results to estimates of Coveyou and Jansson as well as a mathematical demonstration of a so-called rule of thumb related to the choice of ₁ for small k.Due to the number of parameters in this class of generators, it may be possible to obtain increased control over the statistical behavior of these pseudo-random sequences both analytically as well as computationally.     

广义Hausdorf矩中基函数的唯一性

本文通过定义左连续单调函数的广义反函数，讨论了形式为ａｎ＝∫ｂａΨ（ｘ）ｆｎ（ｘ）ｄｘ，ｎ＝１，２，３，…（１）的广义Ｈａｕｓｄｏｒｆ矩的基函数ｆ（ｘ）的唯一性问题。在Ψ（ｘ）为Ｌｅｂｅｓｇｕｅ正可积的条件下，我们证明了当ｆ（ｘ）为单调函数时，满足（１）式的基函数ｆ（ｘ）是唯一的     

Remarks on the Balance Relations for the Two-Dimensional Navier–Stokes Equation with Random Forcing

We use the balance relations for the stationary in time solutions of the randomly forced 2D Navier-Stokes equations, found in [10], to study these solutions further. We show that the vorticity ξ(t,x) of a stationary solution has a finite exponential moment, and that for any the expectation of the integral of over the level-set , up to a constant factor equals the expectation of the integral of over the same set.     

Crystal field effects on the saturation magnetic moment of Sm3+ ion in ferronagnetic samarium compounds

The effects of cubic crystal fields on the saturation magnetic moment of Sm³⁺ ion in ferromagnetic compounds have been investigated. In samarium compounds with magnetic elements, the exchange fieldH _ex acting on Sm³⁺ ion is taken to be proportional to the sublattice magnetization of the magnetic element, while in compounds with nonmagnetic elementsH _ex is taken to be proportional to the spin average of the Sm³⁺ ion and is determined self-consistently. In both types of compoundsH _ex is assumed to be along [001] direction. The saturation magnetic moment is calculated by taking into account the admixture of excited (J=7/2 andJ=9/2) levels into the ground (J=5/2) level of Sm³⁺ ion by crystal fields and exchange fields. It is shown that depending upon the strength, the crystal fields quench or enhance the magnetic moment from the free ion value, and in some cases force Sm³⁺ ion to behave effectively like an (L+S) ion rather than an (L−S)ion. The crystal fields may have important bearing on the performance of samarium compounds as permanent magnet materials.     

A giant enhancement of magnetic moment in a ternary three-shell icosahedral cluster: Fe@Mn12@Au20

ABSTRACT

The average magnetic moment per atom of Mn₁₃ cluster is expected to be enhanced by doping or coating with a shell. Several ternary core–shell icosahedral clusters TM@Mn₁₂@Au₂₀ were constructed by combining substituting the central Mn with VIII elements (Fe, Co, Ni, Ru, Rh, Pd and Pt) and coating with a icosahedral Au₂₀ shell, and systematically studied by using the first-principles density functional method. Compared to Mn₁₃, Fe@Mn₁₂@Au₂₀ cluster shows a giant enhancement on total magnetic moment (52?µ_B) which can be greatly attributed to the ferromagnetic coupling between spin moments of atoms. Coating with Au₂₀ shell enlarged the average distances of TM-Mn and Mn-Mn and is a useful way to change the magnetic coupling style. By analysis of density of states and electron localisation functional, we can conclude that the weak hybridisation between Fe and Mn in Fe@Mn₁₂@Au₂₀ is propitious to maintain their original direction of spin moments of atoms and then form ferromagnetic coupling.     

CASPT2 and CCSD(T) calculations of dipole moments and polarizabilities of acetone in excited states

The acetone molecule is investigated in its ground state and valence ^1,3n-π*, ^1,3π-π*, and ^1,3σ-π* excited states and Rydberg ^1,3n-3s, ^1,3π-3?, ^1,3n-3p_y and ^1,3π-3p_y states using the CASSCF, CASPT2, and CCSD(T) methods. Equilibrium geometries of excited states are obtained and their changes with respect to the ground state are discussed. For most excited states the C_2v symmetry of the ground state is lowered to the C_s symmetry. A series of valence vertical and adiabatic excitation energies is presented along with excitation energies for Rydberg states. The main body of the paper contains Finite-Field Perturbation Theory (FFPT) calculations of electric properties of the vertically as well as geometry relaxed excited states. Dipole moments of valence excited states decrease significantly upon excitation, being about one half of the ground state dipole moment. Polarizabilities usually change upon excitation much less (increase by about 30%) but hyperpolarizabilities are enhanced up to one or two orders of magnitude. The orientation of the dipole moment is reversed in some vertically excited Rydberg states. Properties of the ground and excited states are discussed considering alterations of the electronic structure and shifts in the geometry.     

Quantum chemical studies on (ZnO)n/(NiO)n heterostructured nanoclusters

The structural stability and electronic properties of (ZnO)_n, (NiO)_n, (ZnO)_n/(NiO)_n for n = (1 to 4) and 3D structures were studied using density functional theory. The geometrical optimisation of clusters implies that when the atoms in the cluster increase it leads to an increase in its stability. The stability drastically increases for the heterostructure of (ZnO)_n/(NiO)_n. The dipole moment of the clusters depends on the geometry of the cluster and it is found to be minimum for heterostructures representing more neutralised clusters. HOMO-LUMO energies, ionisation potential, electron affinity, chemical hardness, binding energies and vibrational analysis of different clusters are calculated and reported. The adsorption of CO on the different sites of nanoclusters are studied and discussed.