The binding energies at 0 K of sodium and silver ions to ammonia, methylamine, ethylamine, acetonitrile, and benzonitrile were determined using threshold collision-induced dissociation (CID) and molecular orbital calculations at the ab initio and density functional theory levels, There is good agreement between experimental and calculated binding energies. For the five ligands, threshold CID/CCSD(t)(fu)/6-311++G(2dfp)//MP2(fu)/6-311++G(d,p) Na+ binding energies are the following: ammonia, 25.6 +/- 2.8/24.8; methylamine, 27.0 +/- 1.4/25.9; ethylamine, 27.7 +/- 2.3/27.1; acetonitrile, 30.0 +/- 2.3/30.3; and benzonitrile, 32.7 +/- 1.4/35.0 (B3LYP/6-311++G(d,p)//B3LYP/6-311++G(d,p)) kcal/mol. Threshold CID and B3LYP/DZVP Ag+ binding energies are the following: ammonia, 40.6 +/- 3.0/38.9; methylamine, 41.5 +/- 2.3/41.1; ethylamine, 42.9 +/- 1.4/43.2; acetonitrile, 40.8 +/- 2.0/39.3; and benzonitrile, 41.5 +/- 2.8/43.1 kcal/mol. Wherever comparisons with literature data are possible, the Na+ binding energies determined in this study are in good agreement with established data. For Ag+ binding energies, agreement with the few published theoretical values is not as good. A comparison of Na+ and Ag+ binding energies for the five N-containing ligands in this study and those for water, methanol, and ethanol published earlier (El Aribi, H.; Shoeib, T.; Ling, Y.; Rodriquez, C. F.; Hopkinson, A. C.; Sin, K. W. M. J. Phys. Chem. A 2002, 106, 2908-2914) shows that for every ligand the Ag+ binding energy is higher than the Na+ binding energy. As a group, the amines exhibit the largest differences between Ag+ and Na+ binding energies, followed by the nitriles; the alcohols exhibit the smallest differences. These results are in line with previous observations that Ag+ prefers binding with nitrogen to binding with oxygen.