摘要
利用abinitio计算方法研究了AsF6-阴离子和M+AsF6-(M+=Li+,Na+,K+,Rb+和Cs+)直接接触离子对的结构和光谱行为。结果表明,具有C3V结构三齿相互作用的M+AsF6-最稳定,二齿配位的结构只有在特定条件下才可能稳定存在。当形成离子对后,阳离子与AsF6-的相互作用将改变AsF6-的结构,这其中Li+的影响最大。另外,AsF6-光谱的变化可用来指认溶液中离子的缔合和离子对的种类。
The present paper reports the possible geometries and vibrational spectra of AsF6^- anion and M^+AsF6^-(M^+=Li^+,Na^+,K^+,Rb^+ and Cs^+) contact ion pairs.It was shown that the tridentate C3V structure of M^+AsF6^- was preferred over the monodentate and bidentate geometry.In the tridentate structure,the symmetry of AsF6^- in the coordination is lowered because of the presence of M^+,and its structural parameters and vibrational modes largely differ from its original octahedral structure.The effect of Li+ on the structure of AsF6^- was greater due to its larger charge/radius ratio.The calculated bands for AsF6^- in M^+AsF6^-,located in the range of 600-800 cm^-1,could be used to fingerprint what kind of ion pair was present in solutions.
出处
《光谱学与光谱分析》
SCIE
EI
CAS
CSCD
北大核心
2008年第12期2890-2894,共5页
Spectroscopy and Spectral Analysis
基金
国家自然科学基金项目(20573034)
河南省杰出青年基金项目(074100510005)
河南省高校青年骨干教师资助计划项目资助
关键词
直接接触离子对
六氟砷酸盐
振动光谱
从头计算
Contact ion pair
Hexafluoroarsenate
Vibrational spectra
ab initio calculation