DFT Studies of Indium Nanoclusters, Nanotubes and their Interaction with Molecular Hydrogen
Abstract
Density functional theory calculations have been performed on Indium nanoclusters (Inn, n= 3 to 10) to explore the relative stability among their different isomers and interaction with H2. Geometry optimizations starting from initial candidate geometries were performed for each cluster size, so as to determine a few low energy isomers for each size. Clusters with planar configuration and high symmetry are found to be more stable. For n=8, there comes transition from 2D to 3D structures. Energetically favorable isomers of indium nanoclusters for each size were considered to get H2 adsorbed. In general H2 interaction with these clusters is weak but with those comprising of some odd number of atoms i.e. 5, 7 and 9 is considerable. Indium nanotube also indicates H2 adsorption but Eads increases many folds on introduction of defect in the tube. On the basis of DFT investigations, it is suggested that apparently indium nanoclusters and tubes of specific size seem better candidates for materials to store hydrogen.References
References
J.A. Alonso, “Structure and Properties of Atomic Nanoclustersâ€,
nd Ed., Singapore, World Scientific, 2011.
J.D. Aiken III and R.G. Finke, “A review of modern transition
metal nanoclusters: Their synthesis, characterization, and
applications in catalysisâ€, J. Mol. Catal. A: Chem., vol. 145, no. 1,
pp. 1-44, 1999.
G. Schmid, M. Bäumle, M. Geerkens, I. Heim, C. Osemann and
T. Sawitowski, “Current and future applications of nanoclustersâ€,
Chem. Soc. Rev., vol. 28, no. 3, pp. 179-185, 1999.
F. Baletto and R. Ferrando, “Structural properties of nanoclusters:
Energetic, thermodynamic and kinetic effectsâ€, Rev. Mod. Phys.,
vol. 77, no. 1, pp. 371-426, 2005.
J. P. Wilcoxon and B.L. Abrams, “Critical review synthesis,
structure and properties of metal nanoclustersâ€, Chem. Soc. Rev.,
vol. 35, no. 11, pp. 1162-1194, 2006.
C.R.A. Catlow, S.T. Bromley, S. Hamad, M.M. Fonz, A.A. Sokol
and S.M. Woodley, “Modeling nanoclusters and nucleationâ€, Phys.
Chem. Chem. Phys., vol. 12, no. 4, pp. 786-811, 2010.
R. Ferrando, A. Fortunelli and R.L. Johnston, “Searching for the
optimum structures of alloy nanoclustersâ€, Phys. Chem. Chem.
Phys., vol. 10, no. 5, pp. 640-649, 2008.
T. Pawluk, Y. Hirata and L. Wang, “Studies of iridium
nanoparticles using density functional theory calculationsâ€,
J. Phys. Chem. B, vol. 109, no. 44, pp. 20817-20823, 2005.
S. Nunez and R.L. Johnston, “Structures and chemical ordering of
small Cu−Ag clustersâ€, J. Phys. Chem. C, vol. 114, no. 31,
pp. 13255-13266, 2010.
H. Hakkinen, “Atomic and electronic structure of gold clusters:
understanding flakes, cages and superatoms from simple
conceptsâ€, Chem. Soc. Rev., vol. 37, no. 9, pp. 1847-1859, 2008.
R. Fournier, “Theoretical study of the structure of silver clustersâ€,
J. Chem. Phys., vol. 115, no. 5, pp. 2165-2177, 2001.
Z.H. Li, A.W. Jasper and D.G. Truhlar, “Structures, rugged
energetic landscapes, and nano thermodynamics of Al n (2≤ n≤ 65)
particlesâ€, J. Am. Chem. Soc., vol. 129, no. 48, pp. 14899-14910,
S. Mukhopadhyay, S. Gowtham, R. Pandey and A. Costales,
“Theoretical study of small clusters of indium oxide: InOâ€, J. Mol.
Struc: THEOCHEM, vol. 948, no. 1, pp. 31-35, 2010.
A Walsh, S.M. Woodley, “Evolutionary structure prediction and
electronic properties of indium oxide nanoclustersâ€, Phys. Chem.
Chem. Phys., vol. 12, no. 30, pp. 8446-8453, 2010.
M.A.Taglientea, L. Tapfer, M.V. Antisari, G. Mattei, P. Mazzoldi,
“Synthesis and stability of indium nanoclusters formed in silica by
ion implantationâ€, J. Non-Cryst Solids, vol. 346, no. 10, pp. 663-
, 2004.
F.F Shi, M. Bulkowski and K.C. Hsieh, “Synthesis of indium
nanoclusters and formation of thin film contacts on plastic
substrates for organic and flexible electronics applicationsâ€,
Nanotechnology, vol. 18, no. 26, pp. 265301- 265302, 2007.
O. Stenzel, A. Stendal, M. Roder, C. Borczyskowski, “Tuning of
the plasmon absorption frequency of silver and indium
nanoclusters via thin amorphous silicon filmsâ€, Pure Appl. Opt.,
vol. 6, no. 5, pp. 577-588, 1997.
X.J. Liang, J.L. Li, X. Liu, J.Z. Wang, H. Liu, Q.K. Xue, J.F. Jia,
“Spontaneous assembly of ordered nanoclusters and nanowiresâ€,
Surf. Interface Anal., vol. 36, no. 2, pp. 100-103, 2004.
P.S. Raman, K.G. Nair, R. Kesavamoorthy, B.K. Panigrahi,
S. Dhara and V. Ravichandran, “Formation and growth of
embedded indium nanoclusters by In2+ implantation in silicaâ€,
Appl. Phys. A, vol. 87, no. 4, pp. 709-713, 2007.
N.H. Heo, J.S. Park, Y.J. Kim, W.T. Lim, S.W. Jung and K. Seff,
“Spatially ordered quantum dot array of indium nanoclusters in
fully indium exchanged zeolite Xâ€, J. Phys. Chem. B, vol.107,
no. 5, pp. 1120-1128, 2003.
Y. Zhang, G. Li and L. Zhang, “Synthesis of indium hollow
spheres and nano-tubes by a simple template free solvothermal
processâ€, Inorg. Chem. Commun., vol. 7, no. 3, pp. 344-346, 2004.
S. Kar, S. Santra and S. Chaudhuri, “Direct synthesis of indium
nano-tubes from indium metal sourceâ€, Cryst. Growth Des., vol. 8,
no. 1, pp. 344-346, 2008.
S. Roy and M. Springborg, “Structural and electronic properties of
indium phosphide nano-tubesâ€, J. Phys. Chem. C, vol. 113, no. 1,
pp. 81-86, 2009.
Z. Qian, S. Hou, J. Zhang, R. Li, Z. Shen, X. Zhao and Z. Xue,
“Stability and electronic structure of single walled In nano-tubesâ€,
Physica E, vol. 30, no. 1-2, pp. 81-85, 2005.
P. Jena, “Materials for Hydrogen Storage: Past, Present and
Futureâ€, J. Phys. Chem. Lett. vol. 2, pp. 206-211, 2011.
G. Kresse and J. Hafner, “Ab initio molecular dynamics for liquid
metalsâ€, Phys. Rev. B, vol. 47, no. 1, pp. 558-561, 1993.
J.P. Perdew and Y. Wang, “Accurate and simple analytic
representation of the electron gas correlation energyâ€, Phys. Rev.
B, vol. 45, no. 23, pp. 13244-13249, 1992.
P. E. Blochl, “Projector augmented wave methodâ€, Phys. Rev. B,
vol. 50, no. 24, pp. 17953-17979, 1994.
G. Kresse and D. Joubert, “From ultra soft pseudo potentials to the
projector augmented wave methodâ€, Phys. Rev. B, vol. 59, no. 3,
pp. 1758-1775, 1999.
H.J. Monkhorst and J.D. Pack, “Special points for Brillouin zone
integrationsâ€, Phys. Rev. B, vol. 13, no. 12, pp. 5188-5192, 1976.
M. Methfessel and A.T. Paxton, “High precision sampling for
Brillouin zone integration in metalsâ€, Phys. Rev. B, vol. 40, no. 6,
pp. 3616-3621, 1989.
P. Pulay, “Convergence acceleration of iterative sequences: The
case of scf iterationâ€, Chem. Phys. Lett., vol. 73, no. 2, pp. 393-
, 1980.
J. D. Head, “Computation of vibrational frequencies for adsorbates
on surfacesâ€, Int. J. Quantum Chem., vol. 65, no. 5, pp. 827-838,
T. Björkman, A. Gulans, A. V. Krasheninnikov and R M
Nieminen, “Are we van der Waals ready?â€, J. Phys. Condens.
Matter, vol. 24, pp. 424218-424240, 2012.
R.F.W. Bader, “Atoms in Molecules: A Quantum Theoryâ€, Oxford
University Press, Oxford, 1990.
