【摘要】 依据SiO2掺杂稳定ZrO2溶液中可能存在的各种生长基元及界面反应产物的团簇模型,利用密度泛函理论计算获得了各团簇的结构参数、原子的Mulliken电荷分布、红外活性振动光谱和反应的Gibbs自由能。理论红外光谱分析证实了SiO2/ZrO2界面Si—O—Zr键的形成,同时发现460cm-1左右的特征峰不应归为链状Si—O—Si键的振动,而应是环状Si—O—Si键的振动光谱。此外,Mulliken电荷分布和热力学研究表明:SiO2掺杂稳定的ZrO2四方到单斜相变温度和相变临界尺寸的增加是由于界面Si—O—Zr键的形成降低了与邻近锆配位羟基氧的电荷所致。更多还原

【Abstract】 According to possible growth units and cluster models of interfacial reaction for SiO₂/ZrO₂ binary oxides, the geometric parameters, infrared spectroscopic properties, atomic Mulliken charge distribution and reactive Gibbs free energy of selected silicon and zirconium cluster complexes were obtained by calculation using density-functional theory （DFT）. Theoretical spectroscopic analysis verifies the formation of Si—O—Zr bonds at the interface between SiO₂ and ZrO₂. Furthermore it is found that the characteristic peak around 460 cm^-1 should not be ascribed to the vibration of chain-like Si—O—Si bonds,and it should be the vibration of ring-like Si—O—Si bonds. Moreover, Mulliken charge distribution and thermodynamics analysis show that the increase of temperature and critical size of tetragonal-to-monoclinic phase transformation for SiO₂-doped ZrO₂ are mainly due to the formation of interfacial Si—O—Zr bonds and the decrease of charge of hydroxyl-oxygen close to zirconium coordination.更多还原