Structure and stability of Be6, Be, and Be clusters

The structure and stability of Be6, Be, and Be clusters have been investigated at the B3LYP, B3PW91, and second-order Moller–Plesset (MP2) levels of theory, along with the 6-311G* basis set for neutral and cationic clusters and the 6-311+G* basis set for anion clusters. CCSD(T)/6-311+G* has also been used to calculate some neutral structure to find the most stable structure. Twelve Be6, six Be, and eight Be isomers are identified. The distortion octahedron structure, pentagonal pyramids structure, and trapezoidal bipyramid structure are found to be the most stable structure on the neutral, cationic, and anionic surface, respectively. They are in agreement with the results reported previously. Natural bond orbital (NBO) analysis, molecular orbital (MO) pictures, and the nucleus independent chemical shift (NICS) values suggest aromatic of the neutral and cationic clusters and antiaromatic of the anionic cluster. The multi-center σ bonds and delocalized π bonds play important role in the bonding of the beryllium clusters. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007

[1]  Kangnian Fan,et al.  Density functional theory study of the B6, B6+, B6−, and B62− clusters , 2003 .

[2]  A. Alexandrova,et al.  σ-Aromaticity and σ-Antiaromaticity in Alkali Metal and Alkaline Earth Metal Small Clusters , 2003 .

[3]  C. Zhan,et al.  Electron Affinities of Aln Clusters and Multiple-Fold Aromaticity of the Square Al42- Structure , 2002 .

[4]  Alexander I. Boldyrev,et al.  Theoretical Evidence of Aromaticity in X3− (X = B, Al, Ga) Species , 2002 .

[5]  Lai‐Sheng Wang,et al.  Aromatic Mercury Clusters in Ancient Amalgams , 2001 .

[6]  L. Wang,et al.  On the aromaticity of square planar Ga4(2-) and In4(2-) in gaseous NaGa4- and NaIn4- clusters. , 2001, Journal of the American Chemical Society.

[7]  Lai‐Sheng Wang,et al.  Observation of all-metal aromatic molecules. , 2001, Science.

[8]  M. Beyer,et al.  Density functional calculations of beryllium clusters Ben, n=2–8 , 2000 .

[9]  Lai‐Sheng Wang,et al.  On the origin of planarity in Al5− and Al5 clusters: The importance of a four-center peripheral bond , 2000 .

[10]  R. W. Hall,et al.  Electronic properties of small neutral and charged beryllium clusters , 2000 .

[11]  P. Schleyer,et al.  An Evaluation of the Aromaticity of Inorganic Rings: Refined Evidence from Magnetic Properties , 1997 .

[12]  Paul von Ragué Schleyer,et al.  Nucleus-Independent Chemical Shifts:  A Simple and Efficient Aromaticity Probe. , 1996, Journal of the American Chemical Society.

[13]  K. Lammertsma,et al.  Bond properties of Be3–7 clusters , 1993 .

[14]  J. Almlöf,et al.  Towards the one‐particle basis set limit of second‐order correlation energies: MP2‐R12 calculations on small Ben and Mgn clusters (n=1–4) , 1993 .

[15]  A. Becke.  Density-functional thermochemistry. III. The role of exact exchange , 1993 .

[16]  Wang,et al.  Accurate and simple analytic representation of the electron-gas correlation energy. , 1992, Physical review. B, Condensed matter.

[17]  H. Kato,et al.  Stabilities of small Ben and Bn clusters (4 ≤ n ≤ 8) by vibrational analysis , 1991 .

[18]  Alistair P. Rendell,et al.  Vibrational frequencies for Be3 and Be4 , 1990 .

[19]  G. Scuseria,et al.  Is coupled cluster singles and doubles (CCSD) more computationally intensive than quadratic configuration interaction (QCISD) , 1989 .

[20]  Curtis L. Janssen,et al.  An efficient reformulation of the closed‐shell coupled cluster single and double excitation (CCSD) equations , 1988 .

[21]  John E. Carpenter,et al.  Analysis of the geometry of the hydroxymethyl radical by the “different hybrids for different spins” natural bond orbital procedure , 1988 .

[22]  Parr,et al.  Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. , 1988, Physical review. B, Condensed matter.

[23]  Martin Head-Gordon,et al.  Quadratic configuration interaction. A general technique for determining electron correlation energies , 1987 .

[24]  W. C. Ermler,et al.  Electronic states and geometries of small Be clusters , 1987 .

[25]  Warren J. Hehre,et al.  AB INITIO Molecular Orbital Theory , 1986 .

[26]  L. Pettersson,et al.  The structure of small metal clusters , 1986 .

[27]  N. Handy,et al.  The binding energies of small Be clusters , 1986 .

[28]  D. Plavsic,et al.  Chemical Bonding and Electronic Structure of Small Homonuclear Clusters of Elements of Groups IA, IIA, IIIA and IVA , 1983 .

[29]  G. Pacchioni,et al.  The bond nature of alkaline-earth homonuclear metal clusters investigated with pseudopotential CI method , 1982 .

[30]  R. Bartlett,et al.  A full coupled‐cluster singles and doubles model: The inclusion of disconnected triples , 1982 .

[31]  Michael J. Frisch,et al.  Contribution of triple substitutions to the electron correlation energy in fourth order perturbation theory , 1980 .

[32]  Rodney J. Bartlett,et al.  Many‐body perturbation theory, coupled‐pair many‐electron theory, and the importance of quadruple excitations for the correlation problem , 1978 .

[33]  J. Pople,et al.  Møller–Plesset theory for atomic ground state energies , 1975 .

[34]  M. Plesset,et al.  Note on an Approximation Treatment for Many-Electron Systems , 1934 .

[35]  Alistair P. Rendell,et al.  Theoretical investigations of the structures and binding energies of Ben and Mgn(n=3–5) clusters , 1990 .