First-principles study of the electronic, optical and bonding properties in dolomite

The structural, electronic, optical properties and chemical bonding of dolomite CaMg(CO3)(2) (rhombohedral calcite-type structure) are investigated using plane wave pseudopotential density-functional theory (DFT) method taking the local density approximation (LDA) and the generalized gradient approximation (GGA) as the exchange-correlation energy functional. The structural properties are consistent with the early experimental and theoretical results. The indirect electronic band gap is estimated to be similar to 5.0 eV, which is less than the optical band gap measured from the fundamental absorption edge of similar to 6.0 eV. The optical band gap is also consistent with the experimental band gap of similar calcite-type structure. A noticeable difference for the LDA and GGA derived transition peaks and a significant optical anisotropy are observed in the optical spectra. The analysis of electronic density of states. Mulliken charge and bonding population shows the coexistence of covalent and ionic bonding in the dolomite structure and the results are consistent with previous theoretical calculations. (C) 2010 Elsevier B.V. All rights reserved.