Structures and spectra of iodide-water clusters I-(H2O)n=1-6:: An ab initio study

被引:119
作者
Lee, HM
Kim, KS
机构
[1] Pohang Univ Sci & Technol, Natl Creat Res Initiat Ctr Superfunct Mat, Pohang 790784, South Korea
[2] Pohang Univ Sci & Technol, Dept Chem, Div Mol & Life Sci, Pohang 790784, South Korea
关键词
D O I
10.1063/1.1345511
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
To investigate the structures of I-(H2O)(n = 1-6), extensive ab initio calculations have been carried out. Owing to very flexible potential surfaces of the system (in particular for n = 5 and 6), the lowest energy structures are characterized from various possible low-lying energy conformers. In contrast to some previously reported structures, we find a new lowest energy structure (followed by a few low-lying energy conformers) for n = 5 and four nearly isoenergetic conformers for n=6. These conformers have surface and near-surface structures with the coordination number of 4. The present results provide the information of possible structures in recent profuse experiments of infrared spectra of I-(H2O)(n = 1-6) and charge transfer from the excited iodide ion to water molecules. Our predicted ionization potentials and OH stretching frequencies are in good agreement with the experimental data available, while only the cases of the OH frequencies for n = 4 and the ionization potential for n = 5 need consideration of conformational change by the temperature effect. (C) 2001 American Institute of Physics.
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页码:4461 / 4471
页数:11
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