Do anionic titanium dioxide nano-clusters reach bulk band gap? A density functional theory study.

The electronic properties of both neutral and anionic (TiO2)(n) (n = 1-10) clusters are investigated by extensive density functional theory calculations. The predicted electron detachment energies and excitation gaps of anionic clusters agree well with the original experimental anion photoelectron spectra (APES). It is shown that the old way to analyze APES tends to overestimate vertical excitation gaps (VGA) of large anionic clusters, clue to the nature of multiple electronic origins for the higher APES bands. Moreover, the VGA of anionic TiO2 clusters are evidently smaller than those of neutral clusters, which may also be the case for other metal oxide clusters with high electron affinity. (C) 2010 Wiley Periodicals, Inc. J Comput Chem 31: 2038-2045, 2010