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化学学报
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化学学报 ›› 1999, Vol. 57 ›› Issue (3): 258-263. 上一篇    下一篇

研究论文

低温基质隔离红外光谱和从头算研究CF~2O...IF

陈末华;王雪峰;郑企克   

  1. 复旦大学激光化学研究所.上海(200433)
  • 发布日期:1999-03-15

Matrix isolation IR spectra and Ab initio study of CF~2O...IF complexes

Chen Mohua;Wang Xuefeng;Zheng Qike   

  1. Fudan Univ, Inst Laser Chem.Shanghai(200433)
  • Published:1999-03-15

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在10KAr和Xe基质中测得CF~2O...IF的两种分子间配合物A和B的红外光谱,观察到A和B之间的异构化反应。采用量子化学从头计算,在MP2/LANL2DZ水平上计算得到A和B的平衡构型的结构参数和振动频率。IF与CF~2O的相互作用引起CF~2O的C=O双键伸长、C-F键缩短,导致v~C~=~O的红移和v~C~F~2的蓝移。由势能曲线可看出,A的势能比B高23kJ/mol,表明B比A稳定,升温能够发生A向B的转化。

关键词: 红外分光光度法, 从头计算法, 付里叶变换, 异构化, 卤代烃, 臭氧

Two CF~2O...IF complexes have been found during laser photolysis of CF~3I/O~2 in Ar and Xe matrices. The geometries and fundamental vibrational frequencies of two complexes CF~2O...IF(A) and CF~2O...IF (B) have been determined by ab initio calculations at MP2 level with the LANL2DZ basis set. The calculated potential energies indicate that the complex(b) is more stable than the complex(A) by 23kJ/mol. The frequencies and stability are in agreement with the experimental results.

Key words: INFRARED SPECTROPHOTOMETRY, AB INITIO CALCULATION, FOURIER TRANSFORM, ISOMERIZATION, HALOHYDROCARBON, OZONE

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