Stability, Infrared Spectra and Electronic Structures of (ZrO 2 ) n ( n =3–6) Clusters: DFT Study

The stability, infrared spectra and electronic structures of (ZrO 2 ) n ( n =3–6) clusters have been investigated by using density‐functional theory (DFT) at B3LYP/6‐31G* level. The lowest‐energy structures have been recognized by considering a number of structural isomers for each cluster size. It is found that the lowest‐energy (ZrO 2 ) 5 cluster is the most stable among the (ZrO 2 ) n ( n =3–6) clusters. The vibration spectra of ZrO stretching motion from terminal oxygen atom locate between 900 and 1000 cm −1 , and the vibrational band of ZrOZrO four member ring is obtained at 600–700 cm −1 , which are in good agreement with the experimental results. Mulliken populations and NBO charges of (ZrO 2 ) n clusters indicate that the charge transfers occur between 4d orbital of Zr atoms and 2p orbital of O atoms. HOMO‐LUMO gaps illustrate that chemical stabilities of the lowest‐energy (ZrO 2 ) n ( n =3–6) clusters display an even‐odd alternating pattern with increasing cluster size.