Hybrid particle‐field molecular dynamics simulations: Parallelization and benchmarks

The parallel implementation of a recently developed hybrid scheme for molecular dynamics (MD) simulations (Milano and Kawakatsu, J Chem Phys 2009, 130, 214106) where self‐consistent field theory (SCF) and particle models are combined is described. Because of the peculiar formulation of the hybrid method, considering single particles interacting with density fields, the most computationally expensive part of the hybrid particle‐field MD simulation can be efficiently parallelized using a straightforward particle decomposition algorithm. Benchmarks of simulations, including comparisons of serial MD and MD‐SCF program profiles, serial MD‐SCF and parallel MD‐SCF program profiles, and parallel benchmarks compared with efficient MD program GROMACS 4.5.4 are tested and reported. The results of benchmarks indicate that the proposed parallelization scheme is very efficient and opens the way to molecular simulations of large scale systems with reasonable computational costs. © 2012 Wiley Periodicals, Inc.     

Synthesis and characterisation of advanced UHMWPE/silver nanocomposites for biomedical applications

A supercritical fluid (SCF) route for facile and homogeneous introduction of silver nanoparticles into polymer hosts is described. Our focus is on ultra-high molecular weight polyethylene (UHMWPE). We demonstrate that the metallic nanoparticles have a substantial effect upon the wear and tribochemical properties of the polymer substrate.     

四苯硼阴离子电子结构的理论研究

分别应用半经验发子轨道理论的AM1方法和在HF／3－21G水平上的从头算分子轨道法,对四苯硼阴离子的电子结构进行了研究。采用解析梯度技术对四苯硼阴离子的平衡态几何构型进行了全优化,得到了分子轨道、电荷布居、静电势以及红外光谱和紫外光谱等参数,计算结果表明：四苯硼阴离子的静电势分布均匀,其前线轨道能级间隔为12．1398eV,利用组态相互作用法得到的紫外光谱跃迁吸收峰主要位于远紫外区,说明四苯硼离子比较稳定,从头算法得到的红外光谱吸收峰分布与实验结果一致,AM1法得到的红外吸收频率与实验值更接近。     

Modification of Guest and Saunders open shell SCF equations to exclude BSSE from molecular interaction calculations

The self-consistent field (SCF) for molecularinteractions algorithm, particularly devised to compute intermolecular interactions, is extended to the case in which one of the two interacting fragments is an open shell system. The method excludes the basis set superposition error in an a priori fashion. To preserve the simplicity of the standard SCF procedure, Guest and Saunders equations concerning the open shell fragment are modified at the cost of a negligible complication with respect to the usual algorithm. Received: 27 May 1997 / Accepted: 29 May 1998 / Published online: 18 September 1998     

A new theory for symmetry orbital and tensor (Ⅱ)——Symmetric reduction of molecular integrals and self-consistent field calculations

The symmetry orbital-symmetry orbital tensor method is applied to the evaluation of molecular integrals (one-electron and two-electron integrals) and the symmetry-orbital-tensor and self-consistent-field (SOT-SCF) calculations. A calculation scheme is proposed to simplify the evaluation of integrals and a key equation is derived to reduce the computation efforts in SCF iterations. According to the key equation, compared with the traditional SCF method, the computation efficiencies including CPU timing and external disk (or internal memory) requirement increase in the magnitude of the square of the order of a point group. The new SOT method is expected to be useful in the theoretical calculations of large molecular systems of high point group symmetries.     

A new theory for symmetry orbital and tensor (II)

The symmetry orbital-symmetry orbital tensor methtd is applied to the evaluation of molecular integrals (one-electron) and two-electron integrals) and the symmetry-orbital-tensor and self-consistent-field (SOT-SCF) calculations. A calculation sheme is proposed to simplify the evaluation of integrals and a key equation is derived to reduce the computation efforts in SCF iterations. According to the key equation, compared with the traditional SCF method, the computation efficiencies including CPU timing and external disk (or internal memory) requirement increase in the magnitude of the square of the order of a point group. The new SOT method is expected to be useful in the theoretical calculations of large molecular systems of high point group symmetries. Projcct supported by the National Natural Science Foundation of China (Grant No. 29473119).     

LFMO和NBO的定域性和作用能解析

为分析苯并分子C12H6的垂直共振能(VRE), 建立了定域片断分子轨道(LFMO)和自然键轨道(NBO)两种基组, 并在两种基组之上进行NBO能量分析和Morokuma能量分解. 在NBO能量分析中, 两种基组的VRE都是稳定的; 而在Morokuma能量分解中, VRE的稳定性取决于基组. 在NBO能量分析中, Fock矩阵的一次性对角化忽视了σ体系和π体系之间的电子耦合作用. 故NBO基组和NBO能量分析方法在计算VRE时似乎都不合理.     

Molecular surface electrostatic potentials in the analysis of non-hydrogen-bonding noncovalent interactions

Electrostatic potentials computed on molecular surfaces are used to analyse some noncovalent interactions that are not in the category of hydrogen bonding, e.g. “halogen bonding”. The systems examined include halogenated methanes, substituted benzenes,s-tetrazine and l,3-bisphenylurea. The data were obtained byab initio SCF calculations.     

On the use of local basis sets for localized molecular orbitals

Two procedures are discussed for the direct variational optimization of localized molecular orbitals which are expanded in local subsets of the molecular basis set. It is shown that a Newton-Raphson approach is more efficient than an iterative diagonalization scheme. The effect of the basis-set truncation on the quality ofab-initio SCF results is investigated for Be, Li₂, HF, H₂O, NH₃, CH₄ and C₂H₆.     

Direct determination of localized SCF orbitals

The determination of SCF molecular orbitals by a perturbation method proposed by Lefebvre and Moser is used for the direct determination of localized SCF orbitals. Comparisons are made with the canonical SCF procedure. Advantages of the present method for conformational studies and for the determination of “local SCF orbitals” are also examined.     

An efficient self-consistent field method for large systems of weakly interacting components

An efficient method for removing the self-consistent field (SCF) diagonalization bottleneck is proposed for systems of weakly interacting components. The method is based on the equations of the locally projected SCF for molecular interactions (SCF MI) which utilize absolutely localized nonorthogonal molecular orbitals expanded in local subsets of the atomic basis set. A generalization of direct inversion in the iterative subspace for nonorthogonal molecular orbitals is formulated to increase the rate of convergence of the SCF MI equations. Single Roothaan step perturbative corrections are developed to improve the accuracy of the SCF MI energies. The resulting energies closely reproduce the conventional SCF energy. Extensive test calculations are performed on water clusters up to several hundred molecules. Compared to conventional SCF, speedups of the order of (N/O)2 have been achieved for the diagonalization step, where N is the size of the atomic orbital basis, and O is the number of occupied molecular orbitals.     

Mixing of generalized parity in molecular orbitals

The concept of generalized parity is introduced. It allows mixing of different symmetries in molecular orbitals in the framework of the Parity Mixing in Orbitals method. An extension of this SCF calculational scheme is also discussed and the relevant secular equations are reported.Alexander von Humboldt Fellow. On leave from the Institute Rudjer Bokovi, Zagreb, Croatia, Yugoslavia.     

Perturbative virtual SCF CI treatment for energy levels of coupled oscillator systems

A perturbative SCF CI treatment to obtain energy levels of coupled oscillator systems is proposed. The method uses the virtual SCF basis set, and the SCF equations are solved by means of a perturbative treatment that provides the diagonal matrix elements involved in the CI calculation. The off-diagonal matrix elements are calculated using a commutation relationship derived from exact quantum theorems. Numerical results for several systems are obtained and compared with those from others SCF, SCF CI , and variational treatments.     

Approximate second order method for orbital optimization of SCF and MCSCF wavefunctions

A quasi-Newton method involving a diagonal guess orbital hessian with iterative updates has been proposed recently by Almlof for the optimization of closed shell self-consistent field (SCF) wavefunctions. The technique is extended in the present work to more general wavefunctions, ranging from open shell SCF through multiconfigurational SCF. A number of examples are presented to show that convergence for closed and open shell SCF rivals conventional direct inversion in the iterative subspace (DIIS). For multiconfigurational SCF wavefunctions, the method presented here requires more iterations than an exact second order program, but since each iteration is substantially faster, leads to a more efficient overall program. Received: 15 August 1996 / Accepted: 22 January 1997     

EDTA-柠檬酸法合成的SrCo0.8Fe0.2O3-δ钙钛矿的结构及制氧性能研究

采用EDTA-柠檬酸联合络合法合成了钙钛矿型金属氧化物SrCo_0.8Fe_0.2O_3-δ(SCF182)粉体。通过XRD和ESEM研究了前驱体溶液不同的pH值对合成的SCF182粉体的晶体结构和微观形貌的影响。并采用固定床实验研究前驱体溶液pH值对SCF182的氧吸附/脱附性能的影响。结果表明,pH值对SCF182晶胞结构和参数影响不大,但影响SCF182的晶粒粒径和微观形貌,当pH值为8的弱碱性条件下时,能够合成蓬松多孔网状纳米结构的钙钛矿粉体。固定床实验显示,前驱体溶液的pH值影响合成的粉体SCF182的氧吸附速率;且SCF182的氧脱附性能随pH值的增大先升高后降低,pH值为8时氧脱附量达到峰值为42.2 mg/g。     

Gradient and mc scf calculations of the conformers and the formation of primary ethylene ozonide

The confonners of primary ethylene ozonide have been studied by ab initio gradient and MC SCF calculations. At the MC SCF level they are more spread in energy than in SCF calculations. The planar conformer, carbon-carbon half chair and the oxygen envelope are much higher m energy than the other conformers. The MC SCF activation energy for cyclo-addition of ozone and ethylene is 91–99 $\text{kJ}\text{mole}$.     

Thermomechanical and shape memory properties of SCF/SBS/LLDPE composites

A thermally triggered shape memory polymer composite was prepared by blending short carbon fiber (SCF) into a blend of poly(styrene-b-butadiene-b-styrene) triblock copolymer (SBS)/linear low density polyethylene (LLDPE) prior to curing. These composites have excellent processability compared with other thermosets. The dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC) were investigated to assess the thermomechanical properties of the SCF/SBS/LLDPE composite. Scanning electron microscope (SEM) imaging of the samples was performed to show the distribution of the SCF in the composite. The study specifically focused on the effect of SCF on the shape memory behavior of the SCF/SBS/LLDPE composite. The results indicated that the large amount of SCF significantly improved the mechanical property of the polymer composites while not damaging the shape memory performance. The SCF/SBS/LLDPE composites exhibited excellent shape memory behavior when the SCF content was less than 15.0 wt%. Moreover, the shape fixity ratio and shape recovery time of the SCF/SBS/LLDPE composites increased with the SCF content.     

超临界流体回收碳纤维树脂复合材料

碳纤维树脂复合材料回收再利用是碳纤维产业可持续发展的重要一环,因此受到学术界及产业界的广泛关注。 超临界流体回收碳纤维方法是一种高效、清洁,并且对碳纤维性能损伤较小的回收方法。 本文回顾了超临界流体回收碳纤维树脂复合材料研究进展,系统讨论超临界体系、反应条件、催化剂等对树脂降解率、回收碳纤维性能的影响,并对超临界流体回收碳纤维树脂复合材料的未来发展进行了展望。     

Coupled multiconfiguration self-consistent field (MC SCF) perturbation theory

The analytical form of the perturbation theory for the MC SCF method of Veillard and Clementi is presented. The appropriate second-order energy functional which takes into account the self-consistency requirements, leads to a set of coupled first-order perturbed equations determining the perturbed configuration coefficients and orbitals. The second-order energy formula derived from this functional can be given a clear physical interpretation. The present analytical approach is compared with the finite perturbation MC SCF scheme. The possibility of the approximate solution of the coupled MC SCF perturbation equations is also discussed and the so-called uncoupled procedures are devised. In the limit of the single determinant wave function the present formulae are shown to be equivalent to the appropriate Hartree-Fock perturbation results. The differences between the one-configuration SCF and the MC SCF approach are illustrated by the calculation of the electric dipole polarizability of. HZ in the CNDO/2 approximation. It is shown that the one-configuration SCF approaches cannot account for the correct asymptotic properties of the second-order energy for large internuclear distances. This feature of the SCF perturbation theories does not depend on the specific approximations of the CNDO/2 scheme and is corrected by using the MC SCF perturbation theory.     

On the ordering of the ionization energies in N2: A MC SCF study of near-degeneracy effects

Single configuration SCF wavefunctions yield poor results for the order and relative energies of low-lying icnic states of N₂. A multi-configurational SCF (MC SCF) model which takes account of the near degeneracy of a small number of strongly and weakly occupied orbitals corrects the errors of the SCF approach. MC SCF results for N₂ predict the correct ordering and give reasonably accurate results for the three lowest ionization potentials.