递归方法和团簇磁性的计算

介绍了如何应用递归方法将哈密顿矩阵三对角化,从而求得局域态密度 ,并以计算铑团簇的磁矩为例,说明了递归方法在研究团簇的电子结构方面的应用。     

Ground-state geometries and stability of NaMg clusters using ab initio molecular dynamics method

The ground-state geometries, energetics and the stability of ( n =1-12) clusters are studied using ab initio molecular dynamics method. Our results indicate that the ground-state geometries of large clusters () are different from those of clusters where a trivalent impurity Al is added to the same monovalent host Na. Other features observed are an early appearance of 3-dimensional structure and a pentagonal growth path from n =6 up to n =11. As expected, the ground-state geometry of is not an icosahedron but can be viewed as a distorted form of one of the low lying geometries of cluster. In the energetically favored structures impurity atom Mg is never located at the center of the cluster. The stability analysis based on the energetics shows (8 valence electrons) to be the most stable. In addition there is a remarkable even-odd pattern observed in the dissociation energy and the second difference in energy which is absent in earlier studies of and clusters. Received: 16 September 1998 / Received in final form: 15 February 1999     

密度泛函理论的不同方法研究小钨团簇的结构与稳定性

分别利用密度泛函理论的LSDA方法 和B3LYP 方法在有效核势基组(LanL2DZ)水平上系统地研究了Wn(n=2―14)团簇的结构和稳定性. Wn(n=2―14)团簇全局能量最小的最稳定结构被确定. 结果表明：在所讨论的尺寸范围内,LSDA方法比B3LYP 方法得到的平均结合能与一阶能量差分高;大部分Wn团簇在两种方法计算下具有相同的几何结构. 两种方法计算结果均表明：除了W3自旋多重度为3重态外,其余尺寸团簇的自旋多重度均为单重态; n=7的最低能量结构为双戴帽五边环,而非正十面体,n=8—10为笼型结构,n=11—14为扁长型结构. 综合平均结合能、一阶能量差分和二阶能量差分,两种计算方法均表明Wn(n=2―14)团簇具有相同的幻数序列(2, 6, 9 和 13).     

密度泛函理论的不同方法研究小钨团簇的结构与稳定性

分别利用密度泛函理论的LSDA方法和B3LYP 方法在有效核势基组(LanL2DZ)水平上系统地研究了Wn(n=2-14)团簇的结构和稳定性.Wn(n=2-14)团簇全局能量最小的最稳定结构被确定.结果表明:在所讨论的尺寸范围内,LSDA方法比B3LYP 方法得到的平均结合能与一阶能量差分高;大部分Wn(n=2-14) 团簇在两种方法计算下具有相同的几何结构.两种方法计算结果均表明:除了W3自旋多重度为3重态外,其余尺寸团簇的自旋多重度均为单重态;n=7的最低能量结构为双戴帽五边环,而非正十面体,n=8-10为笼型结构,n=11-14为扁长型结构.综合平均结合能、一阶能量差分和二阶能量差分,两种计算方法均表明Wn(n=2-14)团簇具有相同的幻数序列(2,6,9 和 13).     

Study of (Al2O3)n(Ox) clusters with n = 16 and x = 0, 1, 2 from first principles calculations

The ionic and electronic structure of (Al₂O₃)_n(O_x) clusters with n 16 and x = 0, 1, 2 is studied by means of first principles density functional calculations, norm-conserving pseudopotentials and a numerical atomic basis set. The equilibrium geometries have been determined by total energy minimization, starting with several initial geometries for each cluster size. The trends obtained for the atomic arrangements (structural isomers, coordination numbers, disordered versus ordered structures, etc.) and the electronic properties (binding energies, Homo-Lumo gap and dipole moments) are discussed. For most of the oxidized clusters studied here we find that the Homo-Lumo gap and the magnitude of dipole moment of isomeric species can vary drastically.     

InSi_n(n=2-15)团簇结构、稳定性与电子性质的理论研究

使用卡里普索(CALYPSO)结构预测程序并结合密度泛函理论,在B3LYP/GENECP基组水平上,对InSi_n(n=2-15)团簇的几何结构进行优化与计算.结构优化表明:InSi_n团簇的最低能量构型趋于立体结构(n2),且形成In原子戴帽InSi_(n-1)团簇结构.稳定性分析发现InSi_(12)团簇为幻数结构,In原子的掺杂降低了Si_(n+1)团簇的稳定性.团簇中的电荷总是由In原子向Si原子转移.最后讨论了团簇的电子局域密度函数、红外与拉曼光谱.     

New CW FIR laser lines obtained in ammonia pumped by a CO2 laser, using the Stark tuning method

We report fifty seven CW FIR emissions observed in NH₃, by resonant pumping with a CO₂ laser. Exact coincidences between IR absorption lines of the gas and emission lines of the CO₂ laser have been carried out by Stark tuning. IR frequency shifts, up to 30 GHz, have allowed the pumping of forty three NH₃ transitions.These FIR emissions correspond to thirty one different wavelengths in the 50–400 m range; eighteen ones of them are new emitted wavelengths by pumping with the CO₂ laser.     

An efficient and general numerical method to compute steady uniform vortices

Steady uniform vortices are widely used to represent high Reynolds number flows, yet their efficient computation still presents some challenges. Existing Newton iteration methods become inefficient as the vortices develop fine-scale features; in addition, these methods cannot, in general, find solutions with specified Casimir invariants. On the other hand, available relaxation approaches are computationally inexpensive, but can fail to converge to a solution. In this paper, we overcome these limitations by introducing a new discretization, based on an inverse-velocity map, which radically increases the efficiency of Newton iteration methods. In addition, we introduce a procedure to prescribe Casimirs and remove the degeneracies in the steady vorticity equation, thus ensuring convergence for general vortex configurations. We illustrate our methodology by considering several unbounded flows involving one or two vortices. Our method enables the computation, for the first time, of steady vortices that do not exhibit any geometric symmetry. In addition, we discover that, as the limiting vortex state for each flow is approached, each family of solutions traces a clockwise spiral in a bifurcation plot consisting of a velocity-impulse diagram. By the recently introduced “IVI diagram” stability approach [Phys. Rev. Lett. 104 (2010) 044504], each turn of this spiral is associated with a loss of stability for the steady flows. Such spiral structure is suggested to be a universal feature of steady, uniform-vorticity flows.     

An MRI denoising method using image data redundancy and local SNR estimation

This paper presents an LMMSE-based method for the three-dimensional (3D) denoising of MR images assuming a Rician noise model. Conventionally, the LMMSE method estimates the noise-less signal values using the observed MR data samples within local neighborhoods. This is not an efficient procedure to deal with this issue while the 3D MR data intrinsically includes many similar samples that can be used to improve the estimation results. To overcome this problem, we model MR data as random fields and establish a principled way which is capable of choosing the samples not only from a local neighborhood but also from a large portion of the given data. To follow the similar samples within the MR data, an effective similarity measure based on the local statistical moments of images is presented. The parameters of the proposed filter are automatically chosen from the estimated local signal-to-noise ratio. To further enhance the denoising performance, a recursive version of the introduced approach is also addressed. The proposed filter is compared with related state-of-the-art filters using both synthetic and real MR datasets. The experimental results demonstrate the superior performance of our proposal in removing the noise and preserving the anatomical structures of MR images.     

第一性原理对Al_mSi_n(m=1,2;n=1～6)团簇结构与性质的研究

本文运用第一性原理对Al_mSi_n（m=1,2;n=1～6）团簇的结构与性质进行了研究.在BLYP的水平上进行了结构优化和频率分析,得到了团簇的最低能量结构.同时计算和讨论了A1_msi_n团簇的束缚能、总能的二阶能量差分和分裂能以及费米能随原子数的变化.研究结果表明:Al_mSi_n团簇在m+n<4时的几何结构是平面结构,从4个原子开始转为空间的立体结构;除AlSi₃和Al₂Si₂团簇外,Al_mSi_n（m=1,2;n=1～6）团簇的束缚能随原子数增加而减小;分析A1_mSi_n（m=1,2;n=1～6）团簇的二阶能量差分和分裂能发现:在m+n=3,5时,团簇都出现较稳定的结构.     

ALIS: An efficient method to compute high spectral resolution polarized solar radiances using the Monte Carlo approach

An efficient method to compute accurate polarized solar radiance spectra using the (3D) Monte Carlo model MYSTIC has been developed. Such high resolution spectra are measured by various satellite instruments for remote sensing of atmospheric trace gases. ALIS (Absorption Lines Importance Sampling) allows the calculation of spectra by tracing photons at only one wavelength. In order to take into account the spectral dependence of the absorption coefficient a spectral absorption weight is calculated for each photon path. At each scattering event the local estimate method is combined with an importance sampling method to take into account the spectral dependence of the scattering coefficient. Since each wavelength grid point is computed based on the same set of random photon paths, the statistical error is almost same for all wavelengths and hence the simulated spectrum is not noisy. The statistical error mainly results in a small relative deviation which is independent of wavelength and can be neglected for those remote sensing applications, where differential absorption features are of interest.Two example applications are presented: The simulation of shortwave-infrared polarized spectra as measured by GOSAT from which CO₂ is retrieved, and the simulation of the differential optical thickness in the visible spectral range which is derived from SCIAMACHY measurements to retrieve NO₂. The computational speed of ALIS (for 1D or 3D atmospheres) is of the order of or even faster than that of one-dimensional discrete ordinate methods, in particular when polarization is considered.     

Structures,energetics and vibrational spectra of (H2O)32 clusters: a journey from model potentials to correlated theory

Empirical model potentials are found to be very useful for generating most competitive minima of large water clusters, whereas correlated (e.g. second order-Møller–Plesset perturbation (MP2) theory or higher) calculations are necessary for predicting their accurate energetics and vibrational features. The present study reports the structures and energetics of (H₂O)₃₂ clusters at MP2 level using aug-cc-pvDZ basis set, starting with low-lying structures generated from model potentials. Such high-end and accurate calculations are made feasible by the cost-effective fragment-based molecular tailoring approach (MTA) in conjunction with the grafting procedure. The latter is found to yield electronic energies with a sub-millihartree accuracy with reference to their full calculation counterparts. The vibrational spectra of nine low-lying (H₂O)₃₂ isomers are obtained from the corresponding MTA-based Hessian matrix. All these low-lying isomers show almost similar spectral features, which are in fair agreement with the experiment. The experimental spectrum of (H₂O)₃₂ is thus better understood from the vibrational features of this set of very closely spaced isomers. The present case study of (H₂O)₃₂ clearly demonstrates the efficacy in obtaining accurate structures, energetics and spectra at correlated level of theory by combining model potential-based structures with fragmentation methods.     

Theoretical study on structures of Ga3N, GaN3, Ga3N2 and Ga2N3 clusters

The structures of Ga_3N, GaN_3, Ga_3N_2 and Ga_2N_3 clusters are studied using the full-potential linear-muffin-tin-orbital molecular dynamics (FP-LMTO MD) method. Four structures for Ga_3 N, five structures for GaN_3, nine structures for Ga_3N_2 and nine structures for Ga_2N_3 have been obtained. The most stable structures of these clusters are planar ones. A strong dominance of the N－-N bond over the Ga－-N and Ga－-Ga bonds appears to control the structural skeletons, supporting the previous result obtained by Kandalam and co-workers. The most stable structures of these small GaN clusters displayed semiconductor-like properties through the calculation of the HOMO－LUMO gaps.     

Structure,electronic properties and vibrational spectra of (MgF2)n clusters through a combination of genetic algorithm and DFT-based approach

In this article, we look at the option of using a stochastic optimisation technique, namely genetic algorithm (GA) in association with density functional theory (DFT) to find out the global minimum structures of (MgF₂)_n clusters with the range of n being between 2 and 10. To confirm whether the structures are indeed the acceptable ones, we go on to evaluate several properties like IR spectroscopic modes, vertical excitation energy, cluster formation energy, vertical ionisation potential and the HOMO–LUMO gap. We stress on the fact that an initial estimation of structure using GA, on two empirical potentials (with and without inclusion of polarisation), leads to a very quick convergence to structures which are quite close to the structures obtained from quantum chemical calculations done from the outset, such as using a DFT calculation. The general structural trend of these systems to form three-dimensional networks is also clear from our study. The lowest energy isomers of these clusters show preference for four-membered Mg₂F₂ and six-membered Mg₃F₃ rings. In the IR spectra of (MgF₂)_n clusters, a blueshift of the Mg–F symmetric stretch and a redshift of asymmetric Mg–F stretching as n increases are obtained.     

利用Gupta势结合遗传算法研究ConCu55－n(n=0—55)混合团簇的结构演化及基态能量

采用半经验的Gupta多体势结合遗传算法对Co_nCu_55－n(n=0—55)混合团簇的基态结构和能量进行了研究,发现这些混合团簇的基态结构是在Co₅₅,Cu₅₅单质团簇(Mackay二十面体)的基础之上发生的畸变;从n=0(Cu₅₅)开始,Co原子从中心到表面,从棱到顶点依次、连续替换Cu原子;基态结构与键能较大键的数目及其平均键长有关;Co₁₃Cu₄₂具有最稳定的结构,13个Co原子全部位于团簇内部形成Mackay二十面体对整个团簇的稳定性有显著影响. 关键词： 团簇 结构和能量 Gupta势 遗传算法     

利用变分结合正则化方法对高度计风速资料调整海面风场的研究

利用变分结合正则化方法,对高度计风速资料在无辐散和有辐散两种情形下的背景风场进行调整,同时进行了数值试验.试验表明:高度计风速对背景风场的调整有积极作用,特别是高度计沿轨区域风场调整效果更为明显.对高度计后向散射截面进行了敏感性试验,当后向散射截面存在随机扰动时,利用高度计风速调整海面风场具有较强的抗噪性.最后进行实例试验,结果表明该方法是切实可行的.     

DFT study of structural, electronic and vibrational properties of pure (Al2O3)n (n = 9, 10, 12, 15) and Ni-doped (Al2O3)n (n = 9, 10) clusters

The geometrical, electronic and vibrational properties of pure (Al₂O₃)_n (n = 9, 10, 12, 15) clusters and Ni-doped (Al₂O₃)_9-10 clusters are investigated by density functional theory. There are four different Ni-doped (Al₂O₃)₉ clusters and one Ni-doped (Al₂O₃)₁₀ cluster taken into account. Compared with the pure clusters, the Ni-doped (Al₂O₃)_9-10 clusters have narrower HOMO-LUMO energy gaps. The results indicate that the impurity of Ni atom is mainly responsible for the reduction of the HOMO-LUMO energy gap. One characteristic vibration band at about 1030 cm⁻¹ is found in the vibrational frequencies of the Ni-doped (Al₂O₃)_9-10 clusters, which is caused by the asymmetric Al-O-Al stretching vibration. Another band at around 826 cm⁻¹ involving the characteristic vibration of Ni-O bond is in good agreement with experimental results.     

An accurate, stable and efficient domain-type meshless method for the solution of MHD flow problems

The aim of the present paper is the development of an efficient numerical algorithm for the solution of magnetohydrodynamics flow problems for regular and irregular geometries subject to Dirichlet, Neumann and Robin boundary conditions. Toward this, the meshless point collocation method (MPCM) is used for MHD flow problems in channels with fully insulating or partially insulating and partially conducting walls, having rectangular, circular, elliptical or even arbitrary cross sections. MPC is a truly meshless and computationally efficient method. The maximum principle for the discrete harmonic operator in the meshfree point collocation method has been proven very recently, and the convergence proof for the numerical solution of the Poisson problem with Dirichlet boundary conditions have been attained also. Additionally, in the present work convergence is attained for Neumann and Robin boundary conditions, accordingly. The shape functions are constructed using the Moving Least Squares (MLS) approximation. The refinement procedure with meshless methods is obtained with an easily handled and fully automated manner. We present results for Hartmann number up to 10⁵${10}^5$. The numerical evidences of the proposed meshless method demonstrate the accuracy of the solutions after comparing with the exact solution and the conventional FEM and BEM, for the Dirichlet, Neumann and Robin boundary conditions of interior problems with simple or complex boundaries.     

An efficient method using ultrasound to accelerate aging in crabapple (Malus asiatica) vinegar produced from fresh fruit and its influencing mechanism investigation

In this study, a kind of crabapple vinegar was developed by the method of mixed bacteria fermentation. It showed that the total acids and total esters in the vinegar increased by 30.51% and 22.67%, respectively. Simultaneously, ultrasound was used to treat the vinegar to shorten the time of aging. In addition, the HS-SPME-GC-MS results show that some volatile components had increased significantly, such as total esters, aldehydes and heterocycles. Combining OAV with radar chart of aroma active ingredients, the order of contribution to the characteristic aroma of crabapple vinegar was esters > alcohols > others > acids. Finally, ultrasonic cavitation and hydroxyl radicals were measured to further prove it could accelerate chemical reaction of crabapple vinegar. The results of FTIR showed that the hydrogen-bonded molecules had increased, while free molecules with irritating taste (such as ethanol and acetic acid) had decreased, which made the taste of crabapple vinegar softer. Results have showed that ultrasound is a promising technique for shortening aging time and it also provides the possibility to improve the taste of fruit vinegar.     

An efficient and selective way to new highly functionalized coronands or spiro derivatives using ultrasonic irradiation

A new, selective, straightforward and general method for preparation of highly functionalized coronands or spiro derivatives bearing 1,2-dihydroxyacetophenone unit, under conventional conditions and ultrasonic irradiation, is reported. The reaction setup involves only one step, acylation of an α-chloro-3,4-dihydroxyacetophenone with phthaloyl dichloride derivatives. 1,3- and 1,4-Phthaloyl dichloride derivatives leads to coronands only, while 1,2-phthaloyl dichlorides lead either to coronands or to spiro derivatives. A feasible explanation for the different behavior between conventional and ultrasound methods could be the different reaction mechanism involved in the two procedures: tetrahedral nucleophilic substitution under conventional conditions and radical substitution under ultrasound. Ultrasound induces a remarkable acceleration of the reactions (from days to minutes) and, most significantly, the yields are twice as high. A feasible explanation for the efficiency of the reactions under ultrasonic irradiation is presented.