The stability, infrared spectra and electronic structures of （ZrO2）n （n= 3--6） clusters have been investigated by using density-functional theory （DFT） at B3LYP/6-31 G＊ level. The lowest-energy structures have ...The stability, infrared spectra and electronic structures of （ZrO2）n （n= 3--6） clusters have been investigated by using density-functional theory （DFT） at B3LYP/6-31 G＊ 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 （ZrO2）5 cluster is the most stable among the （ZrO2）n （n=3--6） clusters. The vibration spectra of Zr-O stretching motion from terminal oxygen atom locate between 900 and 1000 cm 1, and the vibrational band of Zr---O--Zr--O 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 （ZrO2）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 （ZrO2）,, （n = 3--6） clusters display an even-odd alternating pattern with increasing cluster size.展开更多
基金Supported by the state Key Development Program for Basic Research of China （2003CB615707） and the National Natural Science Foundation of China （20736005）.
基金Project supported by the National Natural Science Foundation of China （No. 20876005） and the National Basic Research Program of China （No. 2010CB732301 ）.
文摘The stability, infrared spectra and electronic structures of （ZrO2）n （n= 3--6） clusters have been investigated by using density-functional theory （DFT） at B3LYP/6-31 G＊ 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 （ZrO2）5 cluster is the most stable among the （ZrO2）n （n=3--6） clusters. The vibration spectra of Zr-O stretching motion from terminal oxygen atom locate between 900 and 1000 cm 1, and the vibrational band of Zr---O--Zr--O 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 （ZrO2）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 （ZrO2）,, （n = 3--6） clusters display an even-odd alternating pattern with increasing cluster size.
