Theoretical investigations on the chemical bonding, electronic structure, and optical properties of the metal-organic framework MOF-5

Li-Ming Yang; Ponniah Vajeeston; Ponniah Ravindran; Helmer Fjellvåg; Mats Tilset

doi:10.1021/ic100694w

Theoretical investigations on the chemical bonding, electronic structure, and optical properties of the metal-organic framework MOF-5

Inorg Chem. 2010 Nov 15;49(22):10283-90. doi: 10.1021/ic100694w. Epub 2010 Oct 20.

Authors

Li-Ming Yang¹, Ponniah Vajeeston, Ponniah Ravindran, Helmer Fjellvåg, Mats Tilset

Affiliation

¹ Center of Theoretical and Computational Chemistry, Department of Chemistry, University of Oslo, P.O. Box 1033 Blindern, N-0315 Oslo, Norway.

PMID: 20961146
DOI: 10.1021/ic100694w

Abstract

The chemical bonding, electronic structure, and optical properties of metal-organic framework-5 (MOF-5) were systematically investigated using ab initio density functional calculations. The unit cell volume and atomic positions were optimized with the Perdew-Burke-Ernzerhof (PBE) functional leading to a good agreement between the experimental and the theoretical equilibrium structural parameters. The calculated bulk modulus indicates that MOF-5 is a soft material. The estimated band gap from a density of state (DOS) calculation for MOF-5 is about 3.4 eV, indicating a nonmetallic character. As MOFs are considered as potential materials for photocatalysts, active components in hybrid solar cells, and electroluminescence cells, the optical properties of this material were investigated. The detailed analysis of chemical bonding in MOF-5 reveals the nature of the Zn-O, O-C, H-C, and C-C bonds, that is, Zn-O having mainly ionic interaction whereas O-C, H-C, and C-C exhibit mainly covalent interactions. The findings in this paper may contribute to a comprehensive understanding about this kind of material and shed insight into the synthesis and application of novel and stable MOFs.