Current Science

Open Access Open Access  Restricted Access Subscription Access

Al(He)3+N Clusters:A Theoretical Study


Affiliations
1 Department of Chemistry, Cotton University, Panbazar, Guwahati 781 001, India
 

The geometries and electronic structure of molecular ions containing helium (He) atoms complexed to sodium (Na), magnesium (Mg) and aluminium (Al) cations have been studied computationally using density functional and wavefunction-based methods. The complexation of He atoms depends on the charge on the metal centre. While complexation with Na+ and Mg2+ is very weak, that with Al3+ is found to be strong. The highest coordination number (N) for AlHe3+N is found to be 11, which is a true minimum in the potential energy surface. Topological analysis within the realm of quantum theory of atoms in molecules reveals closed-shell interaction in these systems.

Keywords

Al–He Clusters, Cluster, Coordination Number, Complexation, Density Functional, Noble Gases, Wavefunction.
User
Notifications
Font Size

  • Miao, M., Helium chemistry: react with nobility. Nature Chem., 2017, 9, 409–410.

  • Kaltsoyannis, N., Seventeen-coordinate actinide helium complexes, Angew. Chem. Int. Ed., 2017, 56, 7066–7069.

  • Sloane, N. J. A. and Conway, J. H., Sphere Packings, Lattices and Groups, Springer, New York, 1999.

  • Hermann, A., Lein, M., and Schwerdtfeger, P., The search for the species with the highest coordination number. Angew. Chem. Int. Ed., 2007, 46, 2444–2447.

  • Frank, F. C. and Kasper, J. S., Complex alloy structures regarded as sphere Ppackings. I. Definitions and basic principles. Acta Crystallogr., 1958, 11, 184–190.

  • Bichara, C., Pellegatti, A. and Gaspard, J.-P., Properties of liquid group V elements: a numerical tight binding simulation. Phys. Rev. B, 1993, 47, 5002–5007.

  • Johnston, R. L., Atomic and Molecular Clusters, Francis, London, 2002.

  • Komura, Y. and Tokunaga, K., Structural studies of stacking variants in Mg-base Friauf–Laves phases. Acta Crystallogr. Sect. B, 1980, 36, 1548–1554.

  • Dong, X. et al., React with nobility. Nature Chem., 2017, 9, 440-445.

  • Liu, H., Yao, Y., and Klug, D. D., Stable structures of He and H2O at high pressure. Phys. Rev. B, 2015, 91, 014102-7.

  • Hotokka, M., Kindstedt, T., Pyykkö. P. and Roos, B., On bonding in transition-metal helide ions. Mol. Phys., 1984, 52, 23–32.

  • Reho, J. H., Merker, U., Radcliff, M. R., Lehmann, K. K. and Scoles, G., Spectroscopy and dynamics of Al atoms solvated in superfluid helium nanodroplets. J. Phys. Chem. A, 2000, 104, 3620–3626.

  • Jeff, J. et al., Metastable aluminium atoms floating on the surface of helium nanodroplets. Phys. Rev. Lett., 2015, 114, 233401.

  • Perdew, J. P., Burke, K. and Ernzerhof, M., Generalized gradient approximation made simple. Phys. Rev. Lett., 1996, 77, 3865–3868.

  • Chai, J.-D., and Head-Gordon, M., Long-range corrected hybrid density functionals with damped atom–atom dispersion corrections. Phys. Chem. Chem. Phys., 2008, 10, 6615–6620.

  • Perdew, J. P., in Electronic Structure of Solids 1991 (ed. Ziesche, P. and Eschrig, H.), Akademie Verlag, Berlin, 1991, 11; Perdew, J. P., Chevary, J. A., Vosko, S. H., Jackson, K. A., Pederson, M. R., Singh, D. J. and Fiolhais, C., Atoms, molecules, solids, and surfaces: applications of the generalized gradient approximation for exchange and correlation. Phys. Rev. B, 1992, 46, 6671–6687; Perdew, J. P. et al., Erratum: atoms, molecules, solids, and surfaces – applications of the generalized gradient approximation for exchange and correlation. Phys. Rev. B, 1993, 48, 4978.

  • Moller, C. and Plesset, M. S., Note on an approximation treatment for many-electron systems. Phys. Rev., 1934, 46, 618–622; Binkley, J. S. and Pople, J. A., Møller-Plesset theory for atomic ground state energies. Int. J. Quantum Chem., 1975, 9S, 229–236; HeadGordon, M., Pople, J. A. and Frisch, M. J., MP2 energy evaluation by direct methods. Chem. Phys. Lett., 1998, 153, 503–506.

  • Frisch, M. J. et al., Gaussian 16, Revision A.03, Gaussian, Inc, Wallingford CT, USA, 2016.

  • Bader, R. F. W., Atoms in Molecules: A Quantum Theory, Oxford University Press, Oxford, UK, 1990; Bader, R. F. W., A quantum theory of molecular structure and its applications. Chem. Rev., 1991, 91, 893–928.

  • Tian, L., Multiwfn: a multifunctional wavefunction analyser (version 3.1), 2015; http://Multiwfn.codeplex.com; accessed on 22 May 2015).

  • Borocci, S., Giordani, M. and Grandinetti, F., Bonding motifs of noble–gas compounds as described by the local electron energy density. J. Phys. Chem. A, 2015, 119, 6528–6541 and references therein.

  • Shannon, R. D., Acta Crystallogr. Sect. A, 1976, 32, 751.


Abstract Views: 241

PDF Views: 68




  • Al(He)3+N Clusters:A Theoretical Study

Abstract Views: 241  |  PDF Views: 68

Authors

Sabnam S. Ullah
Department of Chemistry, Cotton University, Panbazar, Guwahati 781 001, India
Chayanika Kashyap
Department of Chemistry, Cotton University, Panbazar, Guwahati 781 001, India
Ankur Kanti Guha
Department of Chemistry, Cotton University, Panbazar, Guwahati 781 001, India
Apurba Kr. Barman
Department of Chemistry, Cotton University, Panbazar, Guwahati 781 001, India
Alok Ch. Kalita
Department of Chemistry, Cotton University, Panbazar, Guwahati 781 001, India
Pankaz K. Sharma
Department of Chemistry, Cotton University, Panbazar, Guwahati 781 001, India

Abstract


The geometries and electronic structure of molecular ions containing helium (He) atoms complexed to sodium (Na), magnesium (Mg) and aluminium (Al) cations have been studied computationally using density functional and wavefunction-based methods. The complexation of He atoms depends on the charge on the metal centre. While complexation with Na+ and Mg2+ is very weak, that with Al3+ is found to be strong. The highest coordination number (N) for AlHe3+N is found to be 11, which is a true minimum in the potential energy surface. Topological analysis within the realm of quantum theory of atoms in molecules reveals closed-shell interaction in these systems.

Keywords


Al–He Clusters, Cluster, Coordination Number, Complexation, Density Functional, Noble Gases, Wavefunction.

References





DOI: https://doi.org/10.18520/cs%2Fv114%2Fi10%2F2138-2142