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Global Minimum (global + minimum)
Selected AbstractsSpatial and temporal variations in bank erosion on sand-bed streams in the seasonally wet tropics of northern AustraliaEARTH SURFACE PROCESSES AND LANDFORMS, Issue 9 2006M. J. Saynor Abstract Bank erosion rates and processes across a range of spatial scales are poorly understood in most environments, especially in the seasonally wet tropics of northern Australia where sediment yields are among global minima. A total of 177 erosion pins was installed at 45 sites on four sand-bed streams (Tributaries North and Central, East Tributary and Ngarradj) in the Ngarradj catchment in the Alligator Rivers Region. Bank erosion was measured for up to 3·5 years (start of 1998/99 wet season to end of 2001/02 wet season) at three spatial scales, namely a discontinuous gully (0·6 km2) that was initiated by erosion of a grass swale between 1975 and 1981, a small continuous channel (2·5 km2) on an alluvial fan that was formed by incision of a formerly discontinuous channel between 1964 and 1978, and three medium-sized, continuous channels (8·5,43·6 km2) with riparian vegetation. The bank erosion measurements during a period of average to above-average rainfall established that substantial bank erosion occurred during the wet season on the two smaller channels by rapid lateral migration (Tributary Central) and by erosion of gully sidewalls due to a combination of within-gully flows and overland flow plunging over the sidewalls (Tributary North). Minor bank erosion also occurred during the dry season by faunal activity, by desiccation and loss of cohesion of the sandy bank sediments and by dry flow processes. The larger channels with riparian vegetation (East Tributary and Ngarradj) did not generate significant amounts of sediment by bank erosion. Deposition (i.e. negative pin values) was locally significant at all scales. Bank profile form and channel planform exert a strong control on erosion rates during the wet season but not during the dry season. Copyright © 2006 Commonwealth Government of Australia. [source] Calculated Enthalpies for Dimerisation of Binary, Unsaturated, Main-Group Element Hydrides as a Means to Analyse Their Potential for Multiple BondingEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 11 2003Hans-Jörg Himmel Abstract Herein, the dimerisation of subvalent, binary, main-group element hydrides with the potential for multiple bonding is studied using both hybrid DFT (B3LYP) and ab initio [MP2 and CCSD(T)] methods. The [2+2] cycloaddition is an important and characteristic reaction of derivatives of ethylene. A comparison of dimerisation reactions for several compounds with the potential for multiple bonding should, therefore, shed light on the properties of these species. Our study includes the hydrides E2H2 (E = B, Al, Ga, N P or As), E2H4 (E = C, Si or Ge) and ENH4 (E = B, Al or Ga) and their dimers. Several isomeric forms of the monomers and dimers have to be considered. The trends within a group and a period are established and the factors responsible for them are discussed. It turns out that, generally, the enthalpies for dimerisation increase for heavier homologues, reflecting that the most important factor is the reduced strength of the E,E bonds in the monomers prior to dimerisation and, to some degree, also the reduced ring strain in the cyclic dimers. The exceptions are the dimerisations of B2H2 and Al2H2, both of which lead to the tetrahedral E4H4 species (E = B or Al). Dimerisation of Al2H2 is associated with a smaller enthalpy than that for the dimerisation of B2H2. Comparisons and analyses are made complicated because of the changes in the structures of the isomeric global minima between homologues. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] A hybrid Bayesian back-propagation neural network approach to multivariate modellingINTERNATIONAL JOURNAL FOR NUMERICAL AND ANALYTICAL METHODS IN GEOMECHANICS, Issue 8 2003C. G. Chua Abstract There is growing interest in the use of back-propagation neural networks to model non-linear multivariate problems in geotehnical engineering. To overcome the shortcomings of the conventional back-propagation neural network, such as overfitting, where the neural network learns the spurious details and noise in the training examples, a hybrid back-propagation algorithm has been developed. The method utilizes the genetic algorithms search technique and the Bayesian neural network methodology. The genetic algorithms enhance the stochastic search to locate the global minima for the neural network model. The Bayesian inference procedures essentially provide better generalization and a statistical approach to deal with data uncertainty in comparison with the conventional back-propagation. The uncertainty of data can be indicated using error bars. Two examples are presented to demonstrate the convergence and generalization capabilities of this hybrid algorithm. Copyright © 2003 John Wiley & Sons, Ltd. [source] Global optimization of SixHy at the ab initio level via an iteratively parametrized semiempirical methodINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 4-5 2003Yingbin Ge Abstract Previously we searched for the ab initio global minima of several SixHy clusters by a genetic algorithm in which we used the AM1 semiempirical method to facilitate a rapid energy calculation for the many different cluster geometries explored. However, we found that the AM1 energy ranking significantly differs from the ab initio energy ranking. To better guarantee locating the ab initio global minimum while retaining the efficiency of the AM1 method, we present an improved iterative global optimization strategy. The method involves two separate genetic algorithms that are invoked consecutively. One is the cluster genetic algorithm (CGA), mentioned above, to find the semiempirical SixHy cluster global minimum. A second and separate parametrization genetic algorithm (PGA) is used to reparametrize the AM1 method using some of the ab initio data generated from the CGA to form a training set of different reference clusters but with fixed SixHy stoichiometry. The cluster global optimization search (CGA) and the semiempirical parametrization (PGA) steps are performed iteratively until the semiempirical GA reparametrized AM1 (GAM1) calculations give low-energy optimized structures that are consistent with the globally optimized ab initio structure. We illustrate the new global optimization strategy by attempting to find the ab initio global minima for the Si6H2 and Si6H6 clusters. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2003 [source] Theoretical characterizations of HAsXH (X = N, P, As, Sb, and Bi) isomers in the singlet and triplet statesJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 15 2008Chin-Hung Lai Abstract The lowest singlet and triplet potential energy surfaces for all group 15 HAsXH (X = N, P, As, Sb, and Bi) systems have been explored through ab initio calculations. The geometries of the various isomers were determined at the QCISD/LANL2DZdp level and confirmed to be minima by vibrational analysis. In the case of nitrogen, the global minimum is found to be a triplet H2NAs structure. For the phosphorus case, singlet trans -HAsPH is found to be global minima surrounded by large activation barriers, so that it should be observable. For arsenic, theoretical investigations demonstrate that the stability of HAsAsH isomers decreases in the order singlet trans -HAsAsH > triplet H2AsAs > singlet cis -HAsAsH > triplet HAsAsH > singlet H2AsAs. For antimony and bismuth, the theoretical findings suggest that the stability of HAsXH (X = Sb and Bi) systems decreases in the order triplet H2AsX , singlet trans -HAsXH > singlet cis -HAsXH > triplet HAsXH > triplet H2XAs > singlet H2AsX > singlet H2XAs. Our model calculations indicate that the relativistic effect on heavier group 15 elements should play an important role in determining the geometries as well as the stability of HAsXH molecules. The results obtained are in good agreement with the available experimental data and allow a number of predictions to be made. © 2008 Wiley Periodicals, Inc. J Comput Chem, 2008 [source] Energetic and topological analysis of the reaction of Mo and Mo2 with NH3, C2H2, and C2H4 moleculesJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 13 2004Maria Del Carmen Michelini Abstract The Density functional theory has been applied to characterize the structural features of Mo1,2NH3,C2H4, and C2H2 compounds. Coordination modes, geometrical structures, and binding energies have been calculated for several spin multiplets. It has been shown that in contrast to the conserved spin cases (Mo1,2NH3), the interaction between Mo (or Mo2) and C2H4 (or C2H2) are the low-spin (MoC2H4 and C2H2) and high-spin (Mo2C2H4 and C2H2) complexes. In the ground state of Mo1,2C2H4 and C2H2, the metal-center always reacts with the CC center. The spontaneous formation of the global minima is found to be possible due to the crossing between the potential energy surfaces (ground and excited states with respect to the metallic center). The bonding characterization has been performed using the topological analysis of the Electron Localization Function. It has been shown that the most stable electronic structure for a ,-acceptor ligand correlates with a maximum charge transfer from the metal center to the CC bond of the unsaturated hydrocarbons, resulting in the formation of two new basins located on the carbon atoms (away from hydrogen atoms) and the reduction of the number of attractors of the CC basin. The interaction between Mo1,2 and C2H4 (or C2H2) should be considered as a chemical reaction, which causes the multiplicity change. Contrarily, there is no charge transfer between Mo1,2 and NH3, and the partners are bound by an electrostatic interaction. © 2004 Wiley Periodicals, Inc. J Comput Chem 25: 1647,1655, 2004 [source] On the stability of non-conventional ,-complexes between Ni+ and toluene, phenyl-silane and phenyl-germane,JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 8-9 2006Inés Corral Abstract The complexes between Ni+ and toluene, phenylsilane, and phenylgermane were investigated through the use of high-level density functional theory (DFT) methods. Both harmonic vibrational frequencies and optimized geometries were obtained at the B3LYP/6-311G(d,p) and B3LYP/6-311+G(2df,2p) levels of theory. These results show that at the highest level considered in this work, and in contrast with what was found before for Cu+, the complexes in which Ni+ interacts specifically with only one pair of carbon atoms of the aromatic ring collapse to theconventional ,-complexes. However, similarly to Cu+, non-conventional complex in which the metal ion interacts with the ortho carbon of the aromatic ring and with one of the hydrogen atoms of the XH3 (X,=,Si, Ge) substituent group, through a typical agostic-type interaction are very stable. Nevertheless, whereas for Cu+ these agostic-type complexes are not only the global minima of the potential energy surface but the dominant species in the gas phase, for Ni+ they are slightly less stable than the conventional ,-complexes. Agostic-type complexes exhibit infrared spectra that are markedly different from those of the conventional ,-complexes, and therefore they could be easily identified using this spectroscopic technique. Copyright © 2006 John Wiley & Sons, Ltd. [source] Manganese, Iron, Cobalt, and Nickel Oxo-, Peroxo-, and Superoxoclusters: A Density Functional Theory StudyCHEMPHYSCHEM, Issue 2 2004Ellie L. Uzunova Dr. Abstract The 3d-transition-metal dioxo-, peroxo-, and superoxoclusters with the general composition MO2, M(O2), and MOO (M=Mn, Fe, Co, and Ni) were studied by DFT by the B1LYP functional. The dioxides in their ground states represent the global minima for the M+O2 system. Both ground-state dioxides and the lowest-energy peroxides are in their (d-only) highest spin states. The 6A1 state of Co(O2) exceeds the d-only spin-multiplicity value (quartet), being nearly isoenergetic with the 4A1 state of Co(O2). The energy gain on transforming the peroxides to the corresponding dioxides decreases in the order Mn(O2)>Fe(O2)>Co(O2)>Ni(O2) and varies in the range 0.27,1.8 eV. The dissociation energy to M+O2 for all studied peroxides is less than 1 eV being the lowest (0.47 eV) for Mn(O2). The Mn and Fe peroxides need less than 0.3 eV to rupture one of the MO bonds to form the corresponding superoxide. Mn and Fe superoxides are less stable than the corresponding peroxides; the superoxide of Co is more stable than its peroxide, while Ni superoxide is unstable,its energy is above the limit of dissociation to Ni+O2. According to the electrostatic potential maps, the oxygen atoms in the peroxides are more nucleophilic than those in the dioxides and superoxides, in which the terminal oxygen atom is more nucleophilic than the M-bonded oxygen atom. This result differs from the expectations based on charge-distribution analysis. [source] A peer-to-peer decentralized strategy for resource management in computational GridsCONCURRENCY AND COMPUTATION: PRACTICE & EXPERIENCE, Issue 9 2007Antonella Di Stefano Abstract This paper presents a peer-to-peer (P2P) approach for the management, in a computational Grid, of those resources that are featured by numerical quantity and thus characterized by a coefficient of utilization, such as percentage of CPU time, disk space, memory space, etc. The proposed approach exploits spatial computing concepts and models a Grid by means of a flat P2P architecture consisting of nodes connected by an overlay network; such a network topology, together with the quantity of resource available in each node, forms a three-dimensional surface, where valleys correspond to nodes with a large quantity of available resource. In this scenario, this paper proposes an algorithm for resource discovery that is based on navigating such a surface, in search of the deepest valley (global minimum, that is, the best node). The algorithm, which aims at fairly distributing among nodes the quantity of leased resource, is based on some heuristics that mimic the laws of kinematics. Experimental results show the effectiveness of the algorithm. Copyright © 2006 John Wiley & Sons, Ltd. [source] Integrative optimization by RBF network and particle swarm optimizationELECTRONICS & COMMUNICATIONS IN JAPAN, Issue 12 2009Satoshi Kitayama Abstract This paper presents a method for the integrative optimization system. Recently, many methods for global optimization have been proposed. The objective of these methods is to find a global minimum of nonconvex function. However, large numbers of function evaluations are required, in general. We utilize the response surface method to approximate function space to reduce the function evaluations. The response surface method is constructed from sampling points. The RBF Network, which is one of the neural networks, is utilized to approximate the function space. Then Particle Swarm Optimization (PSO) is applied to the response surface. The proposed system consists of three parts: (Part 1) generation of the sampling points, (Part 2) construction of response surface by RBF Network, (Part 3) optimization by PSO. By iterating these three parts, it is expected that the approximate global minimum of nonconvex function can be obtained with a small number of function evaluations. Through numerical examples, the effectiveness and validity are examined. © 2009 Wiley Periodicals, Inc. Electron Comm Jpn, 92(12): 31,42, 2009; Published online in Wiley InterScience (www.interscience. wiley.com). DOI 10.1002/ecj.10187 [source] Comparison of Isoelectronic Heterometallic and Homometallic Binuclear Cyclopentadienylmetal Carbonyls: The Iron,Nickel vs. the Dicobalt SystemsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 8 2008Jun D. Zhang Abstract The heterometallic binuclear cyclopentadienylironnickel carbonyl compounds Cp2FeNi(CO)n (n = 3, 2, 1; Cp = ,5 -C5H5) have been studied by density functional theory (BP86) for comparison with the isoelectronic homometallic dicobalt derivatives Cp2Co2(CO)n. The FeNi tricarbonyl is shown to be the doubly bridged isomer Cp2Fe(CO)Ni(,-CO)2 with an Fe,Ni distance of 2.455 Å (BP86), in accord with experiment and in contrast to Cp2Co2(CO)3 where singly and triply bridged but not doubly bridged isomers are found. The dicarbonyl compounds Cp2FeNi(,-CO)2 and Cp2Co2(,-CO)2 both have analogous doubly bridged structures with M=M distances around 2.35 Å, suggesting formal M=M double bonds. The monocarbonyl compounds have analogous singly bridged axial structures Cp2FeNi(,-CO) and Cp2Co2(,-CO) with metal,metal distances in the range 2.05 Å (M2 = Co2) to 2.12 Å (M2 = FeNi) consistent with the formal M,M triple bonds required for the favored 18-electron configuration. Open-shell states of Cp2FeNi(,-CO) are found to have even lower energies than the closed-shell structure, which indicates that the ground state of Cp2FeNi(,-CO) might be a high spin structure. However, the global minimum for the monocarbonyl is found to be a singlet "hot dog" perpendicular Cp2NiFe(CO) structure with a terminal CO group bonded to the iron atom. Other higher energy perpendicular structures are also found for Cp2FeNi(CO)n (n = 3, 2, 1) with terminal CO groups and bridging Cp rings. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] On the Structure of Cross-Conjugated 2,3-DiphenylbutadieneEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 28 2007Cornelis A. van Walree Abstract The structure of the cross-conjugated compound 2,3-diphenylbutadiene was investigated by single-crystal X-ray diffraction and computational methods. In the crystal structure the central butadiene fragment adopts an s-gauche geometry [,55.6(2)° torsion angle , around the essential single bond], whereas the styrene moieties are close to planarity. MP2/6-311G* calculations show that the s-gauche conformation represents the global minimum along the , coordinate, but also revealed the existence of an s-trans local minimum. While the crystal structure seems to reflect dominance of styrene-like conjugation, the MP2/6-311G* calculations indicate that conjugation in both the styrene and butadiene ,-systems is important. An NBO orbital deletion study shows that the structure is primarily determined by (hyper)conjugation and that steric effects play a minor role. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] A hybrid fast algorithm for first arrivals tomographyGEOPHYSICAL PROSPECTING, Issue 5 2009Manuela Mendes ABSTRACT A hybrid algorithm, combining Monte-Carlo optimization with simultaneous iterative reconstructive technique (SIRT) tomography, is used to invert first arrival traveltimes from seismic data for building a velocity model. Stochastic algorithms may localize a point around the global minimum of the misfit function but are not suitable for identifying the precise solution. On the other hand, a tomographic model reconstruction, based on a local linearization, will only be successful if an initial model already close to the best solution is available. To overcome these problems, in the method proposed here, a first model obtained using a classical Monte Carlo-based optimization is used as a good initial guess for starting the local search with the SIRT tomographic reconstruction. In the forward problem, the first-break times are calculated by solving the eikonal equation through a velocity model with a fast finite-difference method instead of the traditional slow ray-tracing technique. In addition, for the SIRT tomography the seismic energy from sources to receivers is propagated by applying a fast Fresnel volume approach which when combined with turning rays can handle models with both positive and negative velocity gradients. The performance of this two-step optimization scheme has been tested on synthetic and field data for building a geologically plausible velocity model. This is an efficient and fast search mechanism, which permits insertion of geophysical, geological and geodynamic a priori constraints into the grid model and ray path is completed avoided. Extension of the technique to 3D data and also to the solution of ,static correction' problems is easily feasible. [source] Intramolecular hydrogen bond in 3-imino-propenylamine isomers: AIM and NBO studiesINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 4 2010H. Raissi Abstract The molecular structure and intramolecular hydrogen bond energy of 18 conformers of 3-imino-propenyl-amine were investigated at MP2 and B3LYP levels of theory using the standard 6-311++G** basis set. The atom in molecules or AIM theory of Bader, which is based on the topological properties of the electron density (,), was used additionally and the natural bond orbital (NBO) analysis was also carried out. Furthermore calculations for all possible conformations of 3-imino-propenyl-amin in water solution were also carried out at B3LYP/6-311++G** and MP2/6-311++G** levels of theory. The calculated geometrical parameters and conformational analyses in gas phase and water solution show that the imine,amine conformers of this compound are more stable than the other conformers. B3LYP method predicts the IMA-1 as global minimum. This stability is mainly due to the formation of a strong NH···N intramolecular hydrogen bond, which is assisted by ,-electrons resonance, and this ,-electrons are established by NH2 functional group. Hydrogen bond energies for all conformers of 3-imino-propenyl-amine were obtained from the related rotamers methods. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010 [source] Bonding and correlation analysis of various Si2CO isomers on the potential energy surfaceINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 5 2009Zhong-Jun Zhou Abstract At various levels of theory, singlet and triplet potential energy surfaces (PESs) of Si2CO, which has been studied using matrix isolation infrared spectroscopy, are investigated in detail. A total of 30 isomers and 38 interconversion transition states are obtained at the B3LYP/6-311G(d) level. At the higher CCSD(T)/6-311+G(2d)//QCISD/6-311G(2d)+ZPVE level, the global minimum 11 (0.0 kcal/mol) corresponds to a three-membered ring singlet O-cCSiSi (1A,). On the singlet PES, the species 12 (0.2 kcal/mol) is a bent SiCSiO structure with a 1A, electronic state, followed by a three-membered ring isomer Si-cCSiO (1A,) 13 (23.1 kcal/mol) and a linear SiCOSi 14 (1,+) (38.6 kcal/mol). The isomers 11, 12, 13, and 14 possess not only high thermodynamic stabilities, but also high kinetic stabilities. On the triplet PES, two isomers 31 (3B2) (18.8 kcal/mol) and 37 (3A,) (23.3 kcal/mol) also have high thermodynamic and kinetic stabilities. The bonding natures of the relevant species are analyzed. The similarities and differences between C3O, C3S, SiC2O, and SiC2S are discussed. The present results are also expected to be useful for understanding the initial growing step of the CO-doped Si vaporization processes. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009 [source] Searching the global minimum of a peptide/bilayer potential energy surface by fast heating and cooling cycles of simulated annealingINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 13 2008C. A. Fuzo Abstract The total time reached by molecular dynamics simulation in the study of the interactions between hydrated bilayers and peptides is still very short. A scheme of fast heating and cooling cycles of simulated annealing (FHCCSA) is proposed to improve the efficiency of the search for the global minimum of the peptide/bilayer potential energy surface. In FHCCSA, the high temperatures facilitate the transitions between stable configurations; i.e., heating and cooling cycles make easier the escape of the system outside the local energy minimum. The FHCCSA efficiency is confirmed by comparing its results with conventional NpT simulations. The new scheme saves more than 90% of the total cpu time compared with ordinary NpT simulations. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2008 [source] Study of conformational and optical rotation for the alaninamideINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 4 2007Shulei Zhao Abstract Six stationary points of alaninamide have been located on the potential surface energy (PES) at the B3LYP/6-311++G(2d,2p) level of theory both in the gas phase and in aqueous solution. In the aqueous solution, to take the water solvent effect into account, the polarizable continuum model (PCM) method has been used. Accurate geometric structures and their relative stabilities have been investigated. The results show that the intramolecular hydrogen bond plays a very important role in stabilizing the global minimum of the alaninamide. Moreover, the consistent result in relative energy using high-level computations, including the MP2 and MP3 methods with the same basis set [6-311++G(2d,2p)], indicates that the B3LYP/6-311++G(d,p) level may be applied to the analogue system. More importantly, the optical rotation of the optimized conformers (both in the gas phase and in aqueous solution) of alaninamide have been calculated using the density functional theory (DFT) and Hartree,Fock (HF) method at various basis sets (6-31+G*, 6-311++G(d,p), 6-311++G(2d,2p) and aug-cc-pvdz). The results show that the selection of the computation method and the basis set in calculation has great influence on the results of the optical rotations. The reliability of the HF method is less than that of DFT, and selecting the basis set of 6-311++G(2d,2p) and aug-cc-pvDZ produces relative reliable results. Analysis of the computational results of the structure parameters and the optical rotations yields the conclusion that just the helixes in molecules caused the chiral molecules to be optical active. The Boltzmann equilibrium distributions for the six conformers (both in the gas phase and in the aqueous solution) are also carried out. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 [source] Global optimization of SixHy at the ab initio level via an iteratively parametrized semiempirical methodINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 4-5 2003Yingbin Ge Abstract Previously we searched for the ab initio global minima of several SixHy clusters by a genetic algorithm in which we used the AM1 semiempirical method to facilitate a rapid energy calculation for the many different cluster geometries explored. However, we found that the AM1 energy ranking significantly differs from the ab initio energy ranking. To better guarantee locating the ab initio global minimum while retaining the efficiency of the AM1 method, we present an improved iterative global optimization strategy. The method involves two separate genetic algorithms that are invoked consecutively. One is the cluster genetic algorithm (CGA), mentioned above, to find the semiempirical SixHy cluster global minimum. A second and separate parametrization genetic algorithm (PGA) is used to reparametrize the AM1 method using some of the ab initio data generated from the CGA to form a training set of different reference clusters but with fixed SixHy stoichiometry. The cluster global optimization search (CGA) and the semiempirical parametrization (PGA) steps are performed iteratively until the semiempirical GA reparametrized AM1 (GAM1) calculations give low-energy optimized structures that are consistent with the globally optimized ab initio structure. We illustrate the new global optimization strategy by attempting to find the ab initio global minima for the Si6H2 and Si6H6 clusters. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2003 [source] Robust feedforward design in the presence of LTI/LTV uncertaintiesINTERNATIONAL JOURNAL OF ROBUST AND NONLINEAR CONTROL, Issue 14 2007Gilles Ferreres Abstract A practical method is proposed for the convex design of robust feedforward controllers which ensures H,/L2 performance in the face of LTI and arbitrarily time-varying model uncertainties. A technique that computes the global minimum of this difficult infinite dimensional optimization problem is proposed, as well as a suboptimal but computationally less involved algorithm. Convergence is proved. An efficient way to analyse the robustness properties of a closed loop with or without feedforward controller is obtained as a subproblem. A missile example illustrates the efficiency of the scheme: a robust feedforward controller is designed either on the continuum of linearized time-invariant models (corresponding to trim points) or on a quasi-LPV model representing the non-linear one. Copyright © 2007 John Wiley & Sons, Ltd. [source] Packing identical spheres into a cylinderINTERNATIONAL TRANSACTIONS IN OPERATIONAL RESEARCH, Issue 1 2010Yu. G. Stoyan Abstract The paper deals with the optimization problem of packing identical spheres into a cylinder of minimal height. A mathematical model of the problem is constructed and its characteristics are considered. On the ground of characteristics, a strategy of searching for an approximation to a global minimum is offered. The strategy includes a special search tree construction, a modification of the Zoutendijk method of feasible directions to calculate local minima, and a modification of the decremental neighborhood method to search for an approximation to a global minimum. Numerical examples and performance analysis of solutions are given. On the basis of the mathematical model and numerical experiment, a number of conclusions are drawn. [source] Strain-profile determination in ion-implanted single crystals using generalized simulated annealingJOURNAL OF APPLIED CRYSTALLOGRAPHY, Issue 5-1 2010Alexandre Boulle A novel least-squares fitting procedure is presented that allows the retrieval of strain profiles in ion-implanted single crystals using high-resolution X-ray diffraction. The model is based on the dynamical theory of diffraction, including a B-spline-based description of the lattice strain. The fitting procedure relies on the generalized simulated annealing algorithm which, contrarily to most common least-squares fitting-based methods, allows the global minimum of the error function (the difference between the experimental and the calculated curves) to be found extremely quickly. It is shown that convergence can be achieved in a few hundred Monte Carlo steps, i.e. a few seconds. The method is model-independent and allows determination of the strain profile even without any `guess' regarding its shape. This procedure is applied to the determination of strain profiles in Cs-implanted yttria-stabilized zirconia (YSZ). The strain and damage profiles of YSZ single crystals implanted at different ion fluences are analyzed and discussed. [source] Theoretical characterizations of HAsXH (X = N, P, As, Sb, and Bi) isomers in the singlet and triplet statesJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 15 2008Chin-Hung Lai Abstract The lowest singlet and triplet potential energy surfaces for all group 15 HAsXH (X = N, P, As, Sb, and Bi) systems have been explored through ab initio calculations. The geometries of the various isomers were determined at the QCISD/LANL2DZdp level and confirmed to be minima by vibrational analysis. In the case of nitrogen, the global minimum is found to be a triplet H2NAs structure. For the phosphorus case, singlet trans -HAsPH is found to be global minima surrounded by large activation barriers, so that it should be observable. For arsenic, theoretical investigations demonstrate that the stability of HAsAsH isomers decreases in the order singlet trans -HAsAsH > triplet H2AsAs > singlet cis -HAsAsH > triplet HAsAsH > singlet H2AsAs. For antimony and bismuth, the theoretical findings suggest that the stability of HAsXH (X = Sb and Bi) systems decreases in the order triplet H2AsX , singlet trans -HAsXH > singlet cis -HAsXH > triplet HAsXH > triplet H2XAs > singlet H2AsX > singlet H2XAs. Our model calculations indicate that the relativistic effect on heavier group 15 elements should play an important role in determining the geometries as well as the stability of HAsXH molecules. The results obtained are in good agreement with the available experimental data and allow a number of predictions to be made. © 2008 Wiley Periodicals, Inc. J Comput Chem, 2008 [source] Fitting complex potential energy surfaces to simple model potentials: Application of the simplex-annealing methodJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 6 2005Raúl A. Bustos Marún Abstract A stochastic method of optimization, which combines simulated annealing with simplex, is implemented to fit the parameters of a simple model potential. The main characteristic of the method is that it explores the whole space of the parameters of the model potential, and therefore it is very efficient in locating the global minimum of the cost function, in addition to being independent of the initial guess of the parameters. The method is employed to fit the complex intermolecular potential energy surface of the dimer of water, using as a reference the spectroscopic quality anisotropic site,site potential of Feller et al. The simple model potential chosen for its reparameterization is the MCY model potential of Clementi et al. The quality of the fit is assessed by comparing the geometry of the minimum, the harmonic frequencies, and the second virial coefficients of the parameterized potential with the reference one. Finally, to prove more rigorously the robustness of this method, it is compared with standard nonstochastic methods of optimization. © 2005 Wiley Periodicals, Inc. J Comput Chem 26: 523,531, 2005 [source] Molecules for materials: Germanium hydride neutrals and anions.JOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 16 2002Ge2Hn/Ge2H (n = 0, Molecular structures, electron affinities, thermochemistry of GeHn/GeH (n = 0 Abstract The GeHn (n = 0,4) and Ge2Hn (n = 0,6) systems have been studied systematically by five different density functional methods. The basis sets employed are of double-, plus polarization quality with additional s- and p-type diffuse functions, labeled DZP++. For each compound plausible energetically low-lying structures were optimized. The methods used have been calibrated against a comprehensive tabulation of experimental electron affinities (Chemical Reviews 102, 231, 2002). The geometries predicted in this work include yet unknown anionic species, such as Ge2H,, Ge2H, Ge2H, Ge2H, and Ge2H. In general, the BHLYP method predicts the geometries closest to the few available experimental structures. A number of structures rather different from the analogous well-characterized hydrocarbon radicals and anions are predicted. For example, a vinylidene-like GeGeH structure is the global minimum of Ge2H. For neutral Ge2H4, a methylcarbene-like HGë-GeH3 is neally degenerate with the trans -bent H2GeGeH2 structure. For the Ge2H anion, the methylcarbene-like system is the global minimum. The three different neutral-anion energy differences reported in this research are: the adiabatic electron affinity (EAad), the vertical electron affinity (EAvert), and the vertical detachment energy (VDE). For this family of molecules the B3LYP method appears to predict the most reliable electron affinities. The adiabatic electron affinities after the ZPVE correction are predicted to be 2.02 (Ge2), 2.05 (Ge2H), 1.25 (Ge2H2), 2.09 (Ge2H3), 1.71 (Ge2H4), 2.17 (Ge2H5), and ,0.02 (Ge2H6) eV. We also reported the dissociation energies for the GeHn (n = 1,4) and Ge2Hn (n = 1,6) systems, as well as those for their anionic counterparts. Our theoretical predictions provide strong motivation for the further experimental study of these important germanium hydrides. © 2002 Wiley Periodicals, Inc. J Comput Chem 23: 1642,1655, 2002 [source] NEW CLADID AND FLEXIBLE CRINOIDS FROM THE MISSISSIPPIAN (TOURNAISIAN, IVORIAN) OF ENGLAND AND WALESPALAEONTOLOGY, Issue 5 2007THOMAS W. KAMMER Abstract:, The modern study of fossil crinoids began with J. S. Miller who, in 1821, described specimens from southern England, nearby Wales and other regions, and named several common Early Carboniferous genera. Later, in 1950,60, James Wright monographed all known Early Carboniferous crinoids from the British Isles. In spite of such previous scrutiny, we recognize here two new genera among species already described: Glamorganocrinus gen. nov. (type species: Ophiurocrinus gowerensis Wright, 1960) from South Wales and Mendipocrinus gen. nov. (type species: Poteriocrinus latifrons Austin and Austin, 1847) from southern England. These new genera increase the number of advanced cladid genera in the Ivorian Substage of the Tournaisian in western Europe to 18, and the total number of crinoid genera to 36. A review of species assigned to Mespilocrinus has led to the recognition of M. granulifer De Koninck and LeHon, 1854 as a nomen dubium. A new species of Mespilocrinus, M. wrighti sp. nov., is described from the Ivorian of South Wales; this is the most highly derived species of the genus, as based on a phylogenetic analysis including ten species and 13 characters, with Pycnosaccus as the outgroup. A single, well-ordered tree resulted from this analysis. Interpretation of this tree suggests that the centre of evolution for Mespilocrinus was North America, where three species appeared during the Kinderhookian (early Tournaisian), rapidly achieving morphological disparity within the genus. This radiation event was part of the overall explosive radiation of crinoids following the Late Devonian mass extinction event when crinoid diversity was at a global minimum during the Frasnian. Recovery began during the Famennian, followed by an explosive radiation in the Tournaisian. [source] SiBr4, prediction and determination of crystal structuresACTA CRYSTALLOGRAPHICA SECTION B, Issue 3 2009Alexandra K. Wolf For SiBr4 no crystal structures have been reported yet. In this work the crystal structures of SiBr4 were predicted by global lattice-energy minimizations using force-field methods. Over an energy range of 5,kJ,mol,1 above the global minimum ten possible structures were found. Two of these structures were experimentally determined from X-ray synchrotron powder diffraction data: The low-temperature , phase crystallizes in P21/c, the high-temperature , phase in . Temperature-dependant X-ray powder diffraction shows that the phase transition occurs at 168,K. [source] Blind crystal structure prediction of a novel second polymorph of 1-hydroxy-7-azabenzotriazoleACTA CRYSTALLOGRAPHICA SECTION B, Issue 4 2006Harriott Nowell The commercially available peptide coupling reagent 1-hydroxy-7-azabenzotriazole has been shown to crystallize in two polymorphic forms. The two polymorphs differ in their hydrogen-bonding motif, with form I having an (10) dimer motif and form II having a C(5) chain motif. The previously unreported form II was used as an informal blind test of computational crystal structure prediction for flexible molecules. The crystal structure of form II has been successfully predicted blind from lattice-energy minimization calculations following a series of searches using a large number of rigid conformers. The structure for form II was the third lowest in energy with form I found as the global minimum, with the energy calculated as the sum of the ab initio intramolecular energy penalty for conformational distortion and the intermolecular lattice energy which is calculated from a distributed multipole representation of the charge density. The predicted structure was sufficiently close to the experimental structure that it could be used as a starting model for crystal structure refinement. A subsequent limited polymorph screen failed to yield a third polymorphic form, but demonstrated that alcohol solvents are implicated in the formation of the form I dimer structure. [source] Polyhedral Structures with Three-, Four-, and Five Fold Symmetry in Metal-Centered Ten-Vertex Germanium ClustersCHEMISTRY - A EUROPEAN JOURNAL, Issue 15 2008Bruce King Prof. Abstract Studies using density functional theory (DFT) at the hybrid B3LYP level indicate that the relative energies of structures with three-fold, four-fold, and five-fold symmetry for centered 10-vertex bare germanium clusters of the general type M@Ge10z depend on the central metal atom M and the skeletal electron count. For M@Ge10 clusters with 20 skeletal electrons the DFT results agree with experimental data on the isoelectronic centered 10-vertex bare metal clusters. Thus the lowest energy structure for Ni@Ge10, isoelectronic with the known Ni@In1010,, is a C3v polyhedron derived from the tetracapped trigonal prism. However, Zn@Ge102+ is isoelectronic with the known cluster Zn@In108,, which has the lowest energy structure, a D4d bicapped square antiprism. For the clusters Ni@Ge102,, Cu@Ge10,, and Zn@Ge10 that have 22 skeletal electrons the lowest energy structures are the D4d bicapped square antiprism predicted by the Wade,Mingos rules. For the clusters Ni@Ge104,, Cu@Ge103,, and Zn@Ge102, that have 24 skeletal electrons the lowest energy structures are C3v polyhedra with 10 triangular faces and 3 quadrilateral faces derived from a tetracapped trigonal prism by extreme lengthening of the edges of the capped triangular face of the underlying trigonal prism. For the clusters Cu@Ge105, and Zn@Ge104, that have 26 skeletal electrons the lowest energy structures are the D5d pentagonal antiprisms predicted by the Wade,Mingos rules and the C3v tetracapped trigonal prism as a somewhat higher energy structure. However, for the isoelectronic Ni@Ge106, the relative energies of these two structure types are reversed so that the C3v tetracapped trigonal prism becomes the global minimum. The effects of electron count on the geometries of the D5d pentagonal prism and D4d bicapped square antiprism centered metal cluster structures are consistent with the bonding/antibonding characteristics of the corresponding HOMO and LUMO frontier molecular orbitals. [source] Potential Energy Landscape for Conformationally Gated Secondary Ubiquinone Binding in the Photosynthetic Reaction Center of Rhodobacter SphaeroidesCHEMPHYSCHEM, Issue 2 2004Asif Rahaman Migration of the secondary ubiquinone, UQB, to a site proximal to His-L190 was proposed to be rate-determining for electron transfer in bacterial photosynthetic reaction centers (shown). This study shows that 1) the proximal binding site is the global minimum on the potential energy landscape, 2) multiple minima exist, in qualitative agreement with various binding sites observed in X-ray diffraction studies, and 3) the energy barrier for direct migration of UQB and migration gated by a protein conformational change both agree with the activation energy measured for electron transfer. [source] DFT Studies of the Molecular Structures and Conformational Processes of 1,2-, 1,3- and 1,4-DithiepaneCHINESE JOURNAL OF CHEMISTRY, Issue 3 2008Mina HAGHDADI Abstract In this study density functional theory (DFT) calculations at B3LYP/6-31G(d), B3LYP/6-31+G(d) and B3LYP/6-311+G(2df,2p) levels for geometry optimization and total energy calculation were applied for investigation of the important energy-minimum conformations and transition-state of 1,2-, 1,3-, and 1,4-dithiepanes. Moreover, ab initio calculations at HF/6-31G(d) level of theory for geometry optimization and MP2/6-311G(d)//HF/ 6-31G(d) level for a single-point total energy calculation were reported for different conformers. The obtained results reveal that, the twist-chair conformer is a global minimum for all of these compounds. Also, two local minimum were found in each case, which are twisted-chair and twisted-boat conformers. The boat and chair geometries are transition states. The minimum energy conformation of 1,2-dithiepane is more stable than the lowest energy forms of 1,3-dithiepane and 1,4-dithiepane. Furthermore, the anomeric effect was investigated for 1,3-dithiepane by the natural bond orbital method. The computational results of this study shows that all conformers of 1,3-dithiepane have a hypercojugation system. Finally, the 13C NMR chemical shifts for the conformers of 1,4-dithiepane were calculated, which have good correlation with their experimental values. 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