Quantum chemistry of small clusters of elements of groups Ia, Ib, and IIa:  fundamental concepts, predictions, and interpretation of experiments

Bonačić‐Koutecký, Vlasta; Fantucci, Piercarlo; Koutecký, J.

doi:10.1021/cr00005a016

Cited by 610 publications

(318 citation statements)

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“…[4,5] The initial search for the global minima of B 8 , B 8 À , B 9 , and B 9 À and vibrational frequency calculations were performed using analytical gradients with polarized split-valence basis sets (6-311 + G*) and the hybrid method, known as B3LYP. Some geometries and vibrational frequencies were further refined with the multiconfigurational method CASSCF with various active spaces.…”

Section: Methodsmentioning

confidence: 99%

“…[4,5] Figure 1 shows the PES spectra of B 8 À at three photon energies and those of B 9 À at two photon energies. The 193 nm spectrum of B 8 À revealed four distinct features labeled X, A, B, C (Figure 1 b).…”

mentioning

confidence: 99%

“…Combining PES and computational chemistry is a powerful means to elucidate the electronic structure and chemical bonding of novel clusters. [6][7][8] We performed an extensive computational search for the global minimum structures for B 8 , B 8 À , B 8 2À , B 9 , B 9 À by using a hybrid (density functional and HartreeFock) method. We found that all five species have planar wheel structures ( Figure 2): B 8 and B 8 2À are perfect heptagons and B 9 À is a perfect octagon, whereas B 8 À and B 9 have slight in-plane distortions within the heptagonal and octagonal structures, respectively.…”

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confidence: 99%

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Hepta‐ and Octacoordinate Boron in Molecular Wheels of Eight‐ and Nine‐Atom Boron Clusters: Observation and Confirmation

et al. 2003

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Section: Methodsmentioning

confidence: 99%

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confidence: 99%

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Hepta‐ and Octacoordinate Boron in Molecular Wheels of Eight‐ and Nine‐Atom Boron Clusters: Observation and Confirmation

et al. 2003

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“…Various methods are available that can cope with this situation. Some typical applications concern small clusters of groups Ia, Ib and IIa (Bonacic-Koutecky et al 1991), a calculation of U 2 , which shows an almost unbelievably complicated electronic structure (Gagliardi & Roos 2005) or the treatment of Au − 7 (Johansson et al 2008). All these treatments apply wave-function-based procedures, which become too expensive for clusters with more than 10 atoms.…”

Section: Introductionmentioning

confidence: 99%

Quantum chemical treatments of metal clusters

Weigend

Ahlrichs

2010

Phil. Trans. R. Soc. A.

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This work focuses on finding and rationalizing the building principles of clusters with approximately 300 atoms of different types of metals: main group elements (Al, Sn), alkaline earth metals (Mg), transition metals (Pd) and clusters consisting of two different elements (Ir and Pt). Two tools are inevitable for this purpose: (i) quantum chemical methods that are able to treat a given cluster with both sufficient accuracy and efficiency and (ii) algorithms that are able to systematically scan the (3n−6)-dimensional potential surface of an n-atomic cluster for promising isomers. Currently, the only quantum chemical method that can be applied to metal clusters is density functional theory (DFT). Other methods either do not account for the multi-reference character of metal clusters or are too expensive and thus can be applied only to clusters of very few atoms, which usually is not sufficient for studying the building principles. The accuracy of DFT is not known a priori, but extrapolations to bulk values from calculated series of data show satisfying agreement with experimental data. For scans of the potential surface, simulated annealing techniques or genetic algorithms were used for the smaller clusters (approx. 20-30 atoms), and for the larger clusters considerations were restricted to selected packings and shapes. For the mixed-metallic clusters, perturbation theory turned out to be efficient and successful for finding the most promising distributions of the two atom types at the different sites.

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“…Both pure Al and Li clusters have been studied extensively using the SJM, [8][9][10][11][12][13][14] and the measurements follow SJM predictions relatively well in small clusters. There are, however, some properties ͓e.g., high ionization potential ͑IP͒ of small Al clusters 14,15 and ionic geometries of small Li clusters (Nр20) ͑Ref.…”

Section: Introductionmentioning

confidence: 99%

Aluminum-lithium clusters: First-principles simulation of geometries and electronic properties

Akola

Manninen

2002

Phys. Rev. B

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The geometries and electronic properties of small lithium-rich Al N Li 5N (Nϭ1 -6,10) clusters are studied using first-principles simulations. Aluminum ions form a compact inner core configuration in the clusters that changes into a chainlike skeleton embedded in a lithium surrounding as the cluster size increases. This behavior restricts s-p hybridization effects and causes separate s and p bands in the electronic energy spectrum. A significant charge transfer from Li ions and nearby Al ions strengthens ionic Al-Li bonds, while Al-Al bonds gain a more covalent nature. The evolution of some bulk properties of B2 and B32 phases of AlLi alloys is studied by constructing 59-and 145-atom Al N Li M (NϷM ) clusters based on a truncated rhombic dodecahedron. Tetrahedrally coordinated covalent Al-Al bonds of B32 clusters affect the electronic properties and hardness.

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Quantum chemistry of small clusters of elements of groups Ia, Ib, and IIa: fundamental concepts, predictions, and interpretation of experiments

Cited by 610 publications

References 0 publications

Hepta‐ and Octacoordinate Boron in Molecular Wheels of Eight‐ and Nine‐Atom Boron Clusters: Observation and Confirmation

Hepta‐ and Octacoordinate Boron in Molecular Wheels of Eight‐ and Nine‐Atom Boron Clusters: Observation and Confirmation

Quantum chemical treatments of metal clusters

Aluminum-lithium clusters: First-principles simulation of geometries and electronic properties

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