3 research outputs found
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, due 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
Correlated electronic structure theory for challenging systems
The photochemistry of molecules can be investigated computationally, and this provides
great insight into the underlying chemistry and physics. Such computational
approaches are challenging and can pose many difficulties compared to ground state
methodologies. Care must be taken to accurately describe these systems, as some lowlevel
approximate methods can fail.
The geometrical and electronic structures (TiO2)n clusters (n=1-4) have been
investigated. These are of enormous technological interest as wide band-gap
semiconductors yet the nature of electronic transitions in nano-sized clusters has yet to
be fully elucidated. Structures of the neutral closed-shell, radical cationic and radical
anionic clusters at each size are described and rationalised in terms of the pseudo-Jahn-
Teller effect. We have used high-level response theory to set benchmarks for such
systems. The TiO2 monomer is the simplest of the clusters studied yet proves a stern
test for many lower order ab-initio methods. It is shown that high-level methods are
required to properly describe this simple molecule.
The Monte Carlo Configuration Interaction method attempts to combine the power of
Full CI with a scalability that allows it to be used to study much larger systems. It can
be systematically improved and can approach the accuracy of the Full CI method. This
method is applied here to investigate potential energy surfaces and multipole moments
of a range of small but challenging systems