Computational Study of Cage Like (ZnO) 12 Cluster Using Hybrid and Hybrid Meta Functionals Manuel Alberto Flores-Hidalgo, a Daniel Glossman-Mitnik, a D. H. Galvan b and Diana Barraza-Jimenez c, * a Computational Simulation and Modeling, Advanced Materials Research Center, S.C, Miguel de Cervantes 120, Complejo Industrial Chihuahua, Chih. 31109, México b Physical Chemistry Nanomaterials, Nanoscience and Nanotechnology Center, UNAM, Apdo. Postal 2681, Ensenada, Baja California, Mexico c Computational Chemistry, Research Center in Food and Development, A.C., Av. cuarta sur 3820, Fracc. Vencedores del Desierto, Delicias, Chih. 33089, Mexico (Received: Aug. 10, 2012; Accepted: Feb. 6, 2013; Published Online: Apr. 2, 2013; DOI: 10.1002/jccs.201200439) Density Functional Theory employing hybrid and M06 functionals in combination with three different ba- sis sets is used to calculate the ground state of a cage like (ZnO) 12 nanocluster which has been consistently reported as the more stable cluster for its particular size. B3LYP and B3PW91 hybrid functionals com- bined with 6-31+G*, Lanl2dz and SDD basis sets are employed to treat the ZnO molecular system. Alter- natively, three M06 functionals in combination with three basis sets are employed in the nanostructure cal- culations. Results obtained by treating ZnO sodalite cage nanocluster with M06 functionals demonstrated comparable quality to results obtained with hybrid functionals. Within this study, efficient theoretical DFT methods with the widely known hybrid and the recently created M06 meta-hybrid functionals are employed to study nanostructured ZnO. Our resulting parameters provide a fresh approach performance wise on the different theoretical methods to treat transition metal nanostructures, particularly, ZnO nanoclusters geometry and electronic structure. Keywords: Zinc oxide; Nanoclusters; Sodalite; DFT; Theoretical; B3LYP; M06. INTRODUCTION ZnO nanostructures in diverse forms, such as nano- tubes, 1 nanowires, 2 nanosprings, 3 nanobelts, 4 nanorings, 5 nanohelixes, 6 and nanocages 7 represent a great opportunity to develop new materials for opto-electronics, photovol- taics, sensors and other interesting applications. Studies of small ZnO nanoclusters 8 have predicted energetically low lying isomers, such as small nanoclusters in their most sta- ble atomic structure which are interesting because of their discrete electronic structure that confers them special fea- tures (e.g. optical, magnetic, chemical). Properties at the nanostructure level are unique and may change dramati- cally upon modifying the particle size. Theoretical studies of small nanoparticles provide fundamental predictions of the size-dependent limits of bulk-like materials properties. Several studies currently available have reported novel small ZnO nanoclusters, 9 medium size ZnO clusters, 10-14 as well as ZnS nanoclusters. 15 Other teams have worked with (ZnO) n cluster variants including n = 12, such as the case of Al-Sunaidi et al. 16 In their work they report the stable and low energy metastable structures of zinc oxide clusters (ZnO) n with n = 1-32. Most authors that worked with small or medium size ZnO nanoclusters concur that the structure known as sodalite cage, a T h symmetry shaped by eight hexagons and six isolated squares, is the more stable among (ZnO) 12 nanoclusters. Matxain et al., 10 Wang et al., 17 Al-Sunaidi et al., etc. 16 Behrman et al. 18 agreed on sodalite cage is a (ZnO) 12 motif, highlighted sodalite cage as a possible magic number structure. (ZnO) 12 geometry has raised in- creasing interest and has been studied with different meth- odologies like Time-of-flight mass spectra, 19 genetic algo- rithm (GA) simulation, 20,21 all of them including electronic structure methodology. 17,22 Zandler et al. 11 investigated structure stability for a whole range of binary compounds and made useful insight in metal nanostructures. Similar results as in ZnO clusters were observed in other II-VI and III-V binary compound clusters. 23-34 Density functional theory (DFT) has proved great advances in nanomaterials simulation. Some DFT pioneers expressed high hopes re- garding hybrid functionals, 35 for example, Martell and co-workers 36 through extensive testing concluded that the 1082 © 2013 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim J. Chin. Chem. Soc. 2013, 60, 1082-1091 Article * Corresponding author. Tel: +52 (639)474-8400; Fax: +52 (639)474-8704; Email: dbarraza@ciad.mx JOURNAL OF THE CHINESE CHEMICAL SOCIETY