Cation-water interactions. The M[sup +](H[sub 2]O)[sub n] clusters for alkali metals, M = Li, Na, K, Rb, and Cs

Gas-phase binding energies and enthalpies are reported for small M[sup +](H[sub 2]O)[sub n] clusters consisting of an alkali metal cation (Li[sup +], Na[sup +], K[sup +], Rb[sup +], or Cs[sup +]) with one to six water molecules. Ab initio molecular orbital calculations were performed at the RHF and...

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Bibliographic Details
Published in:Journal of physical chemistry (1952) 1995-03, Vol.99:10
Main Authors: Glendening, E.D., Feller, D.
Format: Article
Language:English
Subjects:
400201 - Chemical & Physicochemical Properties
662300 - Specific Interactions, Decays & Processes- (1992-)
990200 - Mathematics & Computers
ALKALI METALS
BINDING ENERGY
CALCULATION METHODS
CATIONS
CESIUM IONS
CHARGED PARTICLES
DATA
ELEMENTS
ENERGY
ENTHALPY
EXPERIMENTAL DATA
GENERAL AND MISCELLANEOUS//MATHEMATICS, COMPUTING, AND INFORMATION SCIENCE
HYDRATION
HYDROGEN COMPOUNDS
INFORMATION
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
INTERACTIONS
ION PAIRS
IONS
LITHIUM IONS
METALS
MOLECULAR ORBITAL METHOD
NUMERICAL DATA
OXYGEN COMPOUNDS
PHYSICAL PROPERTIES
PHYSICS OF ELEMENTARY PARTICLES AND FIELDS
POTASSIUM IONS
RUBIDIUM IONS
SODIUM IONS
SOLVATION
THERMODYNAMIC PROPERTIES
WATER
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Summary:Gas-phase binding energies and enthalpies are reported for small M[sup +](H[sub 2]O)[sub n] clusters consisting of an alkali metal cation (Li[sup +], Na[sup +], K[sup +], Rb[sup +], or Cs[sup +]) with one to six water molecules. Ab initio molecular orbital calculations were performed at the RHF and MP2 levels of theory with split valence basis sets (3-21G, 6-31+G* with effective core potentials for the heavier alkali metals). Comparison with higher level calculations and with experimentally measured bond dissociation energies suggests that the RHF/6-31+G* method provides a reasonable description of cation-water interactions in the smallest (n = 1-3) clusters. Larger clusters, particularly those that involve water-water hydrogen-bonding interactions, require a correlated treatment at the MP2 level. This study serves to calibrate the RHF/6-31+G* and MP2/6-31+G* methods for applications to cation-ligand interactions in more extended systems (e.g., the ion-selective binding of crown ethers and cryptands) for which calculations at higher levels of theory are not currently feasible. 33 refs., 6 figs., 3 tabs.
ISSN:0022-3654
1541-5740
DOI:10.1021/j100010a015