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Trachtman M , Markham GD , Glusker JP , George P , Bock CW
Interactions of metal ions with water: Ab initio molecular orbital studies of structure, bonding enthalpies, vibrational frequencies and charge distributions. 1. Monohydrates
Inorganic Chemistry. 1998 Aug 24;37(17) :4421-4431
PMID: ISI:000075656600038   
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The formation and properties of a wide range of metal ion monohydrates, Mn+-OH2, where n = 1 and 2, have been studied by ab initio molecular orbital calculations at the MP2(FULL)/6- 311++G**//MP2(FULL)/6-311++G** and CCSD(T)(FULL)/6- 311++G**//MP2(FULL)/6-311++G** computational levels. The ions M are from groups 1A, 2A, 3A, and 4A in the second, third, and fourth periods of the periodic table and the first transition series. Structural parameters, vibrational frequencies, bonding enthalpies, orbital occupancies and energies, and atomic charge distributions are reported. Trends in these properties are correlated with the progressive occupancy of the s, p, and d orbitals. Except for K+-OH2 and Ca2+-OH2, the O-H bond lengths and HOH angles are greater in the hydrates than in unbound water. The M-O bond lengths decrease proceeding from group 1A - -> 4A but become larger in proceeding from the second --> fourth period. The bonding enthalpies, Delta H(298)degrees, are found to be inversely linearly dependent on the M-O bond length Mn+ according to equations of the form Delta H(298)degrees = A + B(1/M-O) for n = 1 and n = 2. Within each monohydrate the distribution of atomic charge reveals a small but definite transfer of charge from water to the metal ion. Compared to unbound water there is, in a metal-ion-bound water complex, an increase in the electronic (negative) charge on the oxygen atom, accompanied by a (significantly) larger decrease in the electronic charge on the hydrogen atoms. The bonding of the water molecule, although electrostatic in origin, is thus more complex than a simple interaction between a point charge on the metal ion, and the water dipole.
Times Cited: 18 English Article 115GX INORG CHEM