Kołaski Maciej, Lee Han Myoung, Choi Young Cheol, Kim Kwang S, Tarakeshwar P, Miller Dorothy J, Lisy James M
Department of Chemistry, Pohang University of Science and Technology, San 31, Hyojadong, Namgu, 790-184 Pohang, Korea.
J Chem Phys. 2007 Feb 21;126(7):074302. doi: 10.1063/1.2426339.
The design of cesium-selective ionophores must include the nature of cesium-water interactions. The authors have carried out extensive ab initio and density functional theory calculations of hydrated cesium cations to obtain reasonably accurate energetics, thermodynamic quantities, and IR spectra. An extensive search was made to find the most stable structures. Since water...water interactions are important in the aqua-Cs+ clusters, the authors investigated the vibrational frequency shifts as a function of the number of water molecules and the frequency characteristics with and without the presence of outer-shell water molecules. The predicted vibrational frequencies were then compared with the infrared photodissociation spectra of argon-tagged hydrated cesium cluster ions. This comparison allowed the identification of specific hydrogen-bonding structures present in the experimental spectra.
铯选择性离子载体的设计必须考虑铯与水相互作用的性质。作者对水合铯阳离子进行了广泛的从头算和密度泛函理论计算，以获得合理准确的能量、热力学量和红外光谱。进行了广泛的搜索以找到最稳定的结构。由于水……水相互作用在水合铯离子簇中很重要，作者研究了振动频率随水分子数量的变化以及有无外层水分子时的频率特性。然后将预测的振动频率与氩标记的水合铯簇离子的红外光解离光谱进行比较。这种比较有助于识别实验光谱中存在的特定氢键结构。
