Powered by LatticeGrid

Search Enter term and hit return. Use '*' for as a wildcard.
Markham GD, Bock CL, Bock CW
Hydration of the carboxylate group: An ab initio molecular orbital study of acetate-water complexes
Structural Chemistry (1997) 8:293-307.
The hydration of the carboxylate group in the acetate anion has been investigated by performing ab initio molecular orbital calculations on selected conformers of complexes with the form CH3CO2-. nH(2)O . mH(2)O, where n and m denote the number of water molecules in the first and second hydration spheres around the carboxylate group, and n + in less than or equal to 7. The results of RHF/6-31G* optimizations for all the complexes and MP2/6-31+G** optimizations for several one-water complexes are reported. The primary consequence of hydration on the structure of the acetate anion is a decrease in the length of the C-C bond. Enthalpy and free energy changes calculated at the MP2/6-31+G** and MP2/6-311++G** levels are reported for the reactions CH3CO2- + [H2O](p) --> CH3CO2- . nH(2)O . mH(2)O where [H2O](p) is a water cluster containing p water molecules and p = n + m less than or equal to 7. The calculations show that conformers with the lowest enthalpy change on complex formation are often not those with the lowest free energy change, due to a greater entropic loss in complexes with tighter and more favorable enthalpic interactions. Hydrogen bonding of six water molecules directly to the carboxylate group in CH3CO2- is found to account for approximately 40% of the enthalpy change and 37% of the free energy change associated with bulk solvation.
Publication Date: 1997-08-01.
Last updated on Thursday, August 06, 2020