Chapter

Practical Aspects of Computational Chemistry III

pp 151-165

Date:

Structure and Energetics of Polyhedral Oligomeric Silsesquioxane (T8,T10,T12-POSS) Cages with Atomic and Ionic Lithium Species

  • Habib U. RehmanAffiliated withDepartment of Chemistry, Center for Environmental Health Sciences, and HPC² Center for Computational Sciences, Mississippi State University
  • , Steven R. GwaltneyAffiliated withDepartment of Chemistry, Center for Environmental Health Sciences, and HPC² Center for Computational Sciences, Mississippi State University Email author 

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Abstract

The structures of endohedral complexes of polyhedral oligomeric silsesquioxane (POSS) cage molecules (HSiO3/2)8, (HSiO3/2)10, and (HSiO3/2)12, containing either atomic or ionic lithium species are determined using density functional theory with the B3LYP functional and the 6-311G(d,p) and 6-311+G(d,p) basis sets. The structures and stabilities of these nanostructures depend on the cage size and the number and charge of the Li species encapsulated in the (HSiO3/2)8, (HSiO3/2)10, and (HSiO3/2)12 host cages. Li cation encapsulation shows attractive interactions with cage oxygen atoms leading to cage shrinkage. Li anion encapsulation breaks the (HSiO3/2)8 host cage. Stable endohedral POSS cages with varying number of neutral and ionic lithium were identified by calculating their inclusion energies and adiabatic and vertical ionization potentials.