Predicting XAFS scattering path cumulants and XAFS spectra for metals (Cu,Ni, Fe,Ti, Au) using molecular dynamics simulations

The ability of molecular dynamics (MD) simulations to support the analysis of X‐ray absorption fine‐structure (XAFS) data for metals is evaluated. The low‐order cumulants (ΔR, σ², C₃) for XAFS scattering paths are calculated for the metals Cu, Ni, Fe, Ti and Au at 300 K using 28 interatomic potentials of the embedded‐atom method type. The MD cumulant predictions were evaluated within a cumulant expansion XAFS fitting model, using global (path‐independent) scaling factors. Direct simulations of the corresponding XAFS spectra, χ(R), are also performed using MD configurational data in combination with the FEFFab initio code. The cumulant scaling parameters compensate for differences between the real and effective scattering path distributions, and for any errors that might exist in the MD predictions and in the experimental data. The fitted value of ΔR is susceptible to experimental errors and inadvertent lattice thermal expansion in the simulation crystallites. The unadjusted predictions of σ² vary in accuracy, but do not show a consistent bias for any metal except Au, for which all potentials overestimate σ². The unadjusted C₃ predictions produced by different potentials display only order‐of‐magnitude consistency. The accuracy of direct simulations of χ(R) for a given metal varies among the different potentials. For each of the metals Cu, Ni, Fe and Ti, one or more of the tested potentials was found to provide a reasonable simulation of χ(R). However, none of the potentials tested for Au was sufficiently accurate for this purpose.     

Superfluidity and Anderson localisation for a weakly interacting Bose gas in a quasiperiodic potential

Using exact diagonalisation and Density Matrix Renormalisation group (DMRG) approach we analyse the transition to a localised state of a weakly interacting quasi-1D Bose gas subjected to a quasiperiodic potential. The analysis is performed by calculating the superfluid fraction, density profile, momentum distribution and visibility for different periodicities of the second lattice and in the presence (or not) of a weak repulsive interaction. It is shown that the transition is sharper towards the maximally incommensurate ratio between the two lattice periodicities, and shifted to higher values of the second lattice strength by weak repulsive interactions. We also relate our results to recent experiments.     

A general Mobius inversion transform formula for hcp lattices and its application

In this paper,we present a general Mobius inversion transform formula for hcp lattices.This formula can be applied to hcp lattices with a non-ideal c/a value and to obtain the pair potential between atoms in these lattices from the cohesive energy.Also,the three-body interaction among atoms in the lattices can be taken into account in the method.This method gives a useful means to obtain interatomic interactions in the interatomic force model.The method has been applied to zinc,and the pair potential obtained is used to calculate the phonon dispersion relations for some high-symmetry directions.It is found that,by properly considering a three-body interaction,one can acquire satisfactory results.     

基于密度泛函理论的菲分子结构与光谱研究

选用密度泛函理论(DET)中的B3LYP方法,在6-311++G(d,p)下对菲分子结构进行优化,计算了其振动频率、极化率及热力学参数,对比了菲分子实测光谱图,首次对其振动频率进行了完全归属。此外,分析并讨论了其前线分子轨道、分子静电势和密立根布局,获得了HOMO-LUMO能隙、分子静电势分布、原子电荷分布等与分子性质密切相关的重要数据,为后续其他多环芳烃分子的光谱检测技术及其光谱和电子结构的分析提供了理论基础。     

Looking at Fokker-Planck dynamics with a noisy instrument

We consider the class of experiments which can be characterized by a Fokker-PIanck dynamics corresponding to the overdamped motion of a state point in a suitable stochastic potential. We assume that the general form of the potential is known (or can be guessed with reasonable accuracy), but that its parameters are to be determined experimentally by measurements made with a noisy instrument. This possible method for determining the potential parameters, which exploits the system's own internal stochastic motion in order to explore rapidly its available parameter space, is substantially more efficient than traditional methods involving time averages of single point measurements, and yet does not appear to have been previously considered. The method could be important when, for example, the experiment must be completed in a limited time owing either to the expense of the experimental materials or to the temporary stationarity of the preparation, situations which are commonly encountered in experimental biochemistry and biology.     

Slowly moving matter--wave gap soliton propagation in weak random nonlinear potential

We systematically investigate the motion of slowly moving matter--wave gap solitons in a nonlinear potential, produced by the weak random spatial variation of the atomic scattering length. With the weak randomness, we construct an effective-particle theory to study the motion of gap solitons. Based on the effective-particle theory, the effect of the randomness on gap solitons is obtained, and the motion of gap solitons is finally solved. Moreover, the analytic results for the general behaviours of gap soliton motion, such as the ensemble-average speed and the reflection probability depending on the weak randomness are obtained. We find that with the increase of the random strength the ensemble-average speed of gap solitons decreases slowly where the reduction is proportional to the variance of the weak randomness, and the reflection probability becomes larger. The theoretical results are in good agreement with the numerical simulations based on the Gross--Pitaevskii equation.     

Effect of the structure of nitroxyl radicals on the kinetics of their acid‐catalyzed disproportionation

Acid‐catalyzed disproportionation of cyclic nitroxyl radicals R₂NO^? includes the half‐reactions of their oxidation to oxoammonium cations R₂NO⁺ and reduction to hydroxylamines R₂NOH. For many nitroxyl radicals, this reaction is characterized by its ~100% reversibility. Quantitative characteristics of acid–base and redox properties of the whole redox triad may be obtained from research of kinetics and equilibrium of this reaction. Here, we have examined the kinetics for the disproportionation of twenty piperidine‐, pyrroline‐, pyrrolidine‐, and imidazoline nitroxyl radicals in aqueous H₂SO₄, and interpreted it in terms of the excess acidity function X. The rate‐limiting step of this reaction is R₂NO^? oxidation by its protonated counterpart R₂NOH^+?. Kinetic stability of R₂NO^? in acidic media depends on the basicity of nitroxyl group. This basicity is influenced predominantly by protonation of another, more basic group in radical structure, and its proximity to nitroxyl group. The discovered estimates of pK values for radical cations R₂NOH^+? (from ?5.8 to ?12.0) indicate a very low basicity of nitroxyl groups in all commonly used R₂NO^?. For the first time, a linear correlation is obtained between the one‐electron reduction potentials of oxoammonium cations and the basicity of nitroxyl groups of related radicals. Copyright © 2013 John Wiley & Sons, Ltd.     

Formation of a vortex lattice in a rotating BCS Fermi gas

We investigate theoretically the formation of a vortex lattice in a superfluid two-spin component Fermi gas in a rotating harmonic trap, in a BCS-type regime of condensed non-bosonic pairs. Our analytical solution of the superfluid hydrodynamic equations, both for the 2D BCS equation of state and for the 3D unitary quantum gas, predicts that the vortex free gas is subject to a dynamic instability for fast enough rotation. With a numerical solution of the full time dependent BCS equations in a 2D model, we confirm the existence of this dynamic instability and we show that it leads to the formation of a regular pattern of quantum vortices in the gas.     

Accurate calculation of the scattering length for the cooling of hydrogen atoms by lithium atoms

An improved ab initio calculation has been performed for the potential for the LiH a ³Σ⁺ state, using two very large basis sets. The Basis Set Superposition Error (BSSE) correction has been determined for both basis sets and the non-Born-Oppenheimer correction estimated to be negligible. The best potential is approximately 10% deeper than the previous estimate. Vibrational energies and scattering lengths have been calculated for ^6,7LiH(D) with both potentials, with and without the BSSE correction, and also with an estimated potential expected to bracket the true potential. The ⁷LiH scattering length is estimated to be (45 ± 4)a₀ and hence the low-energy cross-section in the best a ³Σ⁺ potential is about half that calculated previously. Enhanced cooling by ⁷Li of trapped H atoms remains feasible. Received 30 April 2001     

Analysis of the escape in systems with four exit channels

In this paper, we have performed a numerical investigation of the escape of a particle from two different dynamical systems with the same number of exit channels. We have chosen specific values of the parameters of the systems so that the openings of the potential well in both systems are approximately of the same size. We have found that, in the galactic system, the distribution of the times of escape follows a sequential pattern that has never been detected before. Moreover, we have proved that this pattern is directly related to the geometry of the stable manifolds to the Lyapunov orbits located at the openings of the potential. Finally, we have shown that the different nature of the two systems affects the way the escape occurs, due to the difference in the geometry of the manifolds to the Lyapunov orbits in both systems.