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Emerging polymorphism in nanostructured TiO 2 : Quantum chemical comparison of anatase, rutile, and brookite clusters
Author(s) -
Gałyńska Marta,
Persson Petter
Publication year - 2013
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.24522
Subject(s) - brookite , anatase , rutile , materials science , density functional theory , cluster (spacecraft) , nanocrystal , titanium dioxide , chemical physics , polymorphism (computer science) , coordination number , titanium , nanotechnology , computational chemistry , chemical engineering , chemistry , photocatalysis , biochemistry , organic chemistry , computer science , genotype , metallurgy , gene , programming language , catalysis , ion , engineering
Density functional theory (DFT) and time‐dependent DFT calculations have been performed on a set of 34 titanium dioxide clusters ((TiO2) n with n ≤ 125) to investigate structural and electronic properties of nanostructured TiO 2 (nano‐TiO 2 ) materials. The investigated clusters include models of the three low‐energy polymorphic forms of TiO 2 anatase, rutile, and brookite. A systematic comparison of clusters of increasing size show clear trends for emerging bulk properties in the investigated systems as the surface‐to‐bulk ratio changes from small clusters dominated by undercoordinated surface atoms to more realistic model nanocrystals with significant bulk components. Differences and similarities in terms of atomic coordination, structural stability, and electronic properties for the three different polymorphic forms of nano‐TiO 2 are discussed. The calculations provide evidence for emerging polymorphism with increasing cluster sizes so that the different TiO 2 forms can be clearly distinguished based on structural characteristics associated with the local bonding environment of the constituent atoms. © 2013 Wiley Periodicals, Inc.