# Lowest-energy structures and electronic properties of Na-Si binary clusters from ab initio global search.

14 Nov 2011-Journal of Chemical Physics (American Institute of Physics)-Vol. 135, Iss: 18, pp 184305-184305

TL;DR: The ground state structures of neutral and anionic clusters of Na(n)Si(m) have been determined using genetic algorithm incorporated in first principles total energy code and it is found that the lowest-energy structures of Na-Na clusters resemble those of the pure Si clusters.

Abstract: The ground state structures of neutral and anionic clusters of NanSim (1 ≤ n ≤ 3, 1 ≤ m ≤ 11) have been determined using genetic algorithm incorporated in first principles total energy code. The size dependence of the structural and electronic properties is discussed in detail. It is found that the lowest-energy structures of NanSim clusters resemble those of the pure Si clusters. Interestingly, Na atoms in neutral NanSim clusters are usually well separated by the Sim skeleton, whereas Na atoms can form Na-Na bonds in some anionic clusters. The ionization potentials, adiabatic electron affinities, and photoelectron spectra are also calculated and the results compare well with the experimental data.

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TL;DR: A brief overview of GO algorithms, though concentrating mainly on genetic algorithm and basin hopping techniques, first in combination with EPs, and details of the implementation and application of these search methods to allow exploration for global minimum cluster structures directly using electronic structure methods and, in particular, density functional theory.

Abstract: Over the past decade, there has been a significant growth in the development and application of methods for performing global optimization (GO) of cluster and nanoparticle structures using first-principles electronic structure methods coupled to sophisticated search algorithms. This has in part been driven by the desire to avoid the use of empirical potentials (EPs), especially in cases where no reliable potentials exist to guide the search toward reasonable regions of configuration space. This has been facilitated by improvements in the reliability of the search algorithms, increased efficiency of the electronic structure methods, and the development of faster, multiprocessor high-performance computing architectures. In this review, we give a brief overview of GO algorithms, though concentrating mainly on genetic algorithm and basin hopping techniques, first in combination with EPs. The major part of the review then deals with details of the implementation and application of these search methods to allow exploration for global minimum cluster structures directly using electronic structure methods and, in particular, density functional theory. Example applications are presented, ranging from isolated monometallic and bimetallic clusters to molecular clusters and ligated and surface supported metal clusters. Finally, some possible future developments are highlighted. © 2013 Wiley Periodicals, Inc.

162 citations

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TL;DR: Most interestingly, V(3)Si(12)(-) exhibits a ferrimagnetic, bicapped hexagonal antiprism wheel-like structure with a total spin of 4 μ(B).

Abstract: Our studies show that VSi12− adopts a V-centered hexagonal prism with a singlet spin state. The addition of the second V atom leads to a capped hexagonal antiprism for V2Si12− in a doublet spin state. Most interestingly, V3Si12− exhibits a ferrimagnetic, bicapped hexagonal antiprism wheel-like structure with a total spin of 4μB.

79 citations

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TL;DR: In this article, a comprehensive genetic algorithm (CGA) was used to find the lowest energy structures of a variety of elemental and compound clusters with different types of chemical bonding and their physical and chemical properties.

Abstract: Cluster, as the aggregate of a few to thousands of atoms or molecules, bridges the microscopic world of atoms and molecules and the macroscopic world of condensed matters. The physical and chemical properties of a cluster are determined by its ground state structure, which is significantly different from its bulk structure and sensitively relies on the cluster size. As a well-known nondeterministic polynomial-time hard problem, determining the ground state structure of a cluster is a challenging task due to the extreme complexity of high-dimensional potential energy surface (PES). Genetic algorithm (GA) is an efficient global optimisation method to explore the PES of clusters. Recently, we have developed a GA-based programme, namely comprehensive genetic algorithm (CGA), and incorporated it with ab initio calculations. Using this programme, the lowest energy structures of a variety of elemental and compound clusters with different types of chemical bonding have been determined, and their physical ...

54 citations

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TL;DR: Electronic structure of La(6)O(9) is discussed by analysis of the frontier molecular orbitals and unpaired spin density distributions of charged clusters and the ground state structure was found to be highly symmetric with point group O(h) and the centered oxygen atom has the coordination number as large as six.

Abstract: Structures of stoichiometric (La(2)O(3))(n) (n = 1-6) clusters have been systematically studied by theoretical calculations Global minimum structures for these clusters are determined by genetic algorithm based global optimizations at density functional level The ground state structure for La(6)O(9) was found to be highly symmetric with point group O(h) and the centered oxygen atom has the coordination number as large as six, which is the same as the highest coordination number of oxygen atoms in bulk La(2)O(3) Analysis of the binding energies shows that La(6)O(9) has a high stability among the studied clusters The energies of the highest occupied∕lowest unoccupied molecular orbitals, vertical ionization energy, and vertical electron affinity of each cluster are provided Electronic structure of La(6)O(9) is discussed by analysis of the frontier molecular orbitals and unpaired spin density distributions of charged clusters

48 citations

##### References

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TL;DR: A simple derivation of a simple GGA is presented, in which all parameters (other than those in LSD) are fundamental constants, and only general features of the detailed construction underlying the Perdew-Wang 1991 (PW91) GGA are invoked.

Abstract: Generalized gradient approximations (GGA’s) for the exchange-correlation energy improve upon the local spin density (LSD) description of atoms, molecules, and solids. We present a simple derivation of a simple GGA, in which all parameters (other than those in LSD) are fundamental constants. Only general features of the detailed construction underlying the Perdew-Wang 1991 (PW91) GGA are invoked. Improvements over PW91 include an accurate description of the linear response of the uniform electron gas, correct behavior under uniform scaling, and a smoother potential. [S0031-9007(96)01479-2] PACS numbers: 71.15.Mb, 71.45.Gm Kohn-Sham density functional theory [1,2] is widely used for self-consistent-field electronic structure calculations of the ground-state properties of atoms, molecules, and solids. In this theory, only the exchange-correlation energy EXC › EX 1 EC as a functional of the electron spin densities n"srd and n#srd must be approximated. The most popular functionals have a form appropriate for slowly varying densities: the local spin density (LSD) approximation Z d 3 rn e unif

117,932 citations

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TL;DR: In this paper, a method for accurate and efficient local density functional calculations (LDF) on molecules is described and presented with results using fast convergent threedimensional numerical integrations to calculate the matrix elements occurring in the Ritz variation method.

Abstract: A method for accurate and efficient local density functional calculations (LDF) on molecules is described and presented with results The method, Dmol for short, uses fast convergent three‐dimensional numerical integrations to calculate the matrix elements occurring in the Ritz variation method The flexibility of the integration technique opens the way to use the most efficient variational basis sets A practical choice of numerical basis sets is shown with a built‐in capability to reach the LDF dissociation limit exactly Dmol includes also an efficient, exact approach for calculating the electrostatic potential Results on small molecules illustrate present accuracy and error properties of the method Computational effort for this method grows to leading order with the cube of the molecule size Except for the solution of an algebraic eigenvalue problem the method can be refined to quadratic growth for large molecules

7,750 citations

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TL;DR: In this paper, the DMol3 local orbital density functional method for band structure calculations of insulating and metallic solids is described and the method for calculating semilocal pseudopotential matrix elements and basis functions are detailed together with other unpublished parts of the methodology pertaining to gradient functionals and local orbital basis sets.

Abstract: Recent extensions of the DMol3 local orbital density functional method for band structure calculations of insulating and metallic solids are described. Furthermore the method for calculating semilocal pseudopotential matrix elements and basis functions are detailed together with other unpublished parts of the methodology pertaining to gradient functionals and local orbital basis sets. The method is applied to calculations of the enthalpy of formation of a set of molecules and solids. We find that the present numerical localized basis sets yield improved results as compared to previous results for the same functionals. Enthalpies for the formation of H, N, O, F, Cl, and C, Si, S atoms from the thermodynamic reference states are calculated at the same level of theory. It is found that the performance in predicting molecular enthalpies of formation is markedly improved for the Perdew–Burke–Ernzerhof [Phys. Rev. Lett. 77, 3865 (1996)] functional.

7,255 citations

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TL;DR: In this paper, a broad range of experiments are reviewed and compared with theory, including the behavior of the mass-abundance spectra, polarizabilities, ionization potentials, photoelectron spectra and optical spectra.

Abstract: The study of simple metal clusters has burgeoned in the last decade, motivated by the growing interest in the evolution of physical properties from the atom to the bulk solid, a progression passing through the domain of atomic clusters. On the experimental side, the rapid development of new techniques for producing the clusters and for probing and detecting them has resulted in a phenomenal increase in our knowledge of these systems. For clusters of the simplest metals, the alkali and noble metals, the electronic structure is dominated by the number of valence electrons, and the ionic cores are of secondary importance. These electrons are delocalized, and the electronic system exhibits a shell structure that is closely related to the well-known nuclear shell structure. In this article the results from a broad range of experiments are reviewed and compared with theory. Included are the behavior of the mass-abundance spectra, polarizabilities, ionization potentials, photoelectron spectra, optical spectra, and fragmentation phenomena.

2,378 citations

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TL;DR: In this paper, a review of the experimental methods for the production of free nanoclusters is presented, along with theoretical and simulation issues, always discussed in close connection with the experimental results.

Abstract: The structural properties of free nanoclusters are reviewed. Special attention is paid to the interplay of energetic, thermodynamic, and kinetic factors in the explanation of cluster structures that are actually observed in experiments. The review starts with a brief summary of the experimental methods for the production of free nanoclusters and then considers theoretical and simulation issues, always discussed in close connection with the experimental results. The energetic properties are treated first, along with methods for modeling elementary constituent interactions and for global optimization on the cluster potential-energy surface. After that, a section on cluster thermodynamics follows. The discussion includes the analysis of solid-solid structural transitions and of melting, with its size dependence. The last section is devoted to the growth kinetics of free nanoclusters and treats the growth of isolated clusters and their coalescence. Several specific systems are analyzed.

1,490 citations