中文摘要：

应用LDA-PWC方法对亚碘酰苯低聚物HO-（PhIO）n-H（n=1-10）（链末端以羟基结束）共10个模型分子进行了理论研究．计算结果表明PhIO分子链大致呈“T”形，I—O链的两个I-O键键长非常接近，同时发现I-O链产生扭转，整个亚碘酰苯低聚物呈螺旋状结构．应用B3LYP法得到HO-（PhIO）6-H更为精确的亚碘酰苯低聚物稳定构型，平均I-O键长为0．2089nm，标准偏差为0．0007nm．理论计算表明在600-400cm^-1段，PhI18O的吸收峰向低波数方向移动，与实验观测结果一致．振动模式分析发现该段吸收峰均涉及氧原子，18O同位素效应将降低各振动峰值的频率．峰值移动最大的吸收峰为591／566em叫（MO／墙o），与之对应的理论计算值为590．409／557．788cm^-1（16O／18O），属于对称伸缩振动V（I-O-I）吸收峰（443／436cm^-1）对应的理论计算值为460．627／439．158cm^-1（16O／18O），归属于不对称伸缩振动V（I—O-I）．

英文摘要：

Ten geometries of iodosylbenzene oligomer HO-（PhIO）n-H （n= 1 -10） model compounds were investigated by LDA-PWC method. The calculated geometries show that the PhlO unit in iodosylbenzene oligomer has a T-shaped structure, and both I-O bond lengths of I-O chain are nearly equal. Due to the torsion of I-O chain, iodosylbenzene oligomer exhibits a helical geometry. To obtain a more accurate and steady geometry, the structure of HO-（PhIO）6-H was also investigated by B3LYP calculations. Results show that the I-O bond mean length is 0.2089 nm with only 0.0007 nm standard deviation. IR spectral calculation results show that the vibrational frequencies between 600-400 cm^-1 will shift to lower frequencies upon the 180 substitution, which is in accordance with the experimental observation. Vibrational mode analysis indicates that these bands are related to oxygen atom vibrations. The observed 180 sensitive IR bands of 591/566 cm^-1 and 443/436 cm^-1 （160/180） correspond to the calculated bands of 590.409/557.788^ -1 cm and 460.627/439.158 cm^-1 （16O/18O） respectively, and the former was ascribed to the symmetric stretching mode v（I-O-I） of iodosylbenzene oligomer, and the latter to the absymmetric stretching mode V（I-O-I）.