Binding energies of the silver ion to small oxygen- containing ligands: Determination by means of density functional theory and threshold collision-induced dissociation

The binding enthalpies at 0 K of the silver ion to water, methanol, ethanol, diethyl ether, and acetone were calculated using density functional theory (DFT) using the hybrid B3LYP level of theory with the DZVP basis set; they were also measured using the threshold collision-induced dissociation (CID) method. There is good agreement between the two sets of data. For the five ligands, the DFT/threshold CID values are: water, 28.1/31.6 +/- 2.5; methanol, 30.1/33.0 +/- 3.7; ethanol, 32.0/33.9 +/- 3.5; diethyl ether, 33.3/33.2 +/- 1.5; and acetone, 36.2/38.0 +/- 1.4 kcal/mol. The average of the absolute differences between the DFT and threshold CID results is 2.0 kcal/mol, a value smaller than the average experimental uncertainty of 2.5 kcal/mol. For identical ligands, the silver ion binding energies are lower than the lithium ion binding energies, but higher than the sodium ion binding energies.