物理化学学报 >> 2004, Vol. 20 >> Issue (11): 1329-1334.doi: 10.3866/PKU.WHXB20041109

研究论文 上一篇    下一篇

用密度泛函方法研究α-[XMo12O40]n－杂多阴离子的振动光谱

李中华;王锐;陈振宁;韦永德;周百斌   

  1. 哈尔滨工业大学应用化学系,哈尔滨　150001
  • 收稿日期:2004-04-15 修回日期:2004-06-18 发布日期:2004-11-15
  • 通讯作者: 李中华 E-mail:lizh@hit.edu.cn

A DFT Study of the Vibrational Frequencies ofα-[XMo12O40]n－ Heteropolyanions

Li Zhong-Hua;Wang Rui;Chen Zhen-Ning;Wei Yong-De;Zhou Bai-Bin   

  1. Department of Applied Chemistry, Harbin Institute of Technology, Harbin　150001
  • Received:2004-04-15 Revised:2004-06-18 Published:2004-11-15
  • Contact: Li Zhong-Hua E-mail:lizh@hit.edu.cn

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摘要： 采用第一性原理密度泛函方法,在考虑极化函数的双数字(DND)基组水平上,对α-[XMo12O40]n－(X=P, Si, Ge)杂多阴离子进行了几何构型优化,得到了与X-ray晶体衍射实验结果相一致的结构参数;并在优化几何构型基础上进行了振动频率分析,首次得到了非经验计算的杂多阴离子的振动光谱,计算的频率及强度与实验结果总体上吻合得较好.对全部22个有红外活性(IR)和44个有拉曼(R)活性的频率进行了指认,并与经验方法得到的结果进行了比较,同时,对部分频率的归属加以进一步的澄清与确认.

关键词: 杂多阴离子, 红外活性, 拉曼活性, 频率分析, 密度泛函理论

Abstract: First-principle density functional theory, at DND basis set level, was used to optimize the structure ofα-[XMo12O40]n－(X=P, Si, Ge). The optimized structure parameters coincide with those obtained by X-ray diffraction. Based on the optimized structure, frequency analyses were carried out by non-empirical method for the first time. In general, the agreement between the experimental vibrational spectra and the calculated values, on both the frequencies and intensities, is good. The assignment for all of the 22 infrared (IR) active and 44 Raman active frequencies is carried out and compared with that obtained by empirical methods. At the same time, a number of previously reported assignments have been conformed or clarified. In addition, the characteristic group frequencies of IR spectra forα-[XMo12O40]n－(X=P, Si, Ge) obey the P >Si >Ge rule, whereas those of Raman spectra are not the case. Meanwhile, a rational interpretation is offered.

Key words: Heteropolyanions, Infrared active, Raman active, Frequency analysis, Density Functional Theory(DFT)