Photoelectron spectroscopy and ab initio calculations of Li(H₂O)n(-) and Cs(H₂O)n(-) (n = 1-6) clusters.
The Li(H2O)n(-) and Cs(H2O)n(-) (n = 0-6) clusters were studied using anion photoelectron spectroscopy combined with ab initio calculations. It was found that Li tends to be surrounded by water molecules with no water-water H-bonds being formed in the first hydration shell; while Cs sticks on the surface of water-water H-bonds network. The Li atom in its anionic or neutral state is surrounded by four water molecules through Li-O interactions within the first hydration shell; while the case of Cs is different. For the anionic Cs(H2O)n(-) clusters, two types of structures, namely H-end and O-end structures, were identified, with nearly degenerate energies. For the neutral Cs(H2O)n clusters, only O-end structures exist and the first hydration shell of the Cs atom has four water molecules. The different hydration nature of Li and Cs atoms can be ascribed to the delicate balance between the alkali metal-water interactions and the water-water interactions as well as the effect of excess electron.
†Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Molecular Reaction Dynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
Zhen
Z
Zeng
‡Beijing National Laboratory for Molecular Sciences, Institute of Theoretical and Computational Chemistry, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China.
Cheng-Wen
CW
Liu
†Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Molecular Reaction Dynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
Gao-Lei
GL
Hou
†Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Molecular Reaction Dynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
Gang
G
Feng
†Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Molecular Reaction Dynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
Hong-Guang
HG
Xu
‡Beijing National Laboratory for Molecular Sciences, Institute of Theoretical and Computational Chemistry, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China.
Yi Qin
YQ
Gao
†Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Molecular Reaction Dynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
Wei-Jun
WJ
Zheng
D002586:Cesium / Q000737:chemistry*; D008094:Lithium / Q000737:chemistry*; D056951:Photoelectron Spectroscopy; D011789:Quantum Theory; D014867:Water / Q000737:chemistry*
D014867:Water; D002586:Cesium; D008094:Lithium