The geometries, energetics, and vibrational spectra are calculated for the two complexes at the SCF and correlated MP2 levels using the 6‐31G∗∗ basis set, augmented by a second set of d functions on Cl. While correlation represents an important factor in the binding of H3 N⋅⋅HCl, it contributes little to the stronger Li bond. Unlike the HCl stretch νs which decreases substantially in frequency and is greatly intensified in H3 N⋅⋅HCl, the frequency of the LiCl stretch undergoes an increase and little change is noted in its intensity, conforming to prior spectral measurements. The intensities of the intramolecular stretching modes of NH3 are greatly strengthened by formation of a H bond and even more so for a Li bond. These intensity patterns are analyzed via atomic polar tensors which reveal that formation of a H bond dramatically lessens the ability of the electron density to shift along with the proton. A stretch of H–Cl hence leads to a large increase in molecular dipole moment. This ‘‘freezing’’ of the electron cloud is much smaller in the Li bond and its effect on the νs intensity is counteracted by a much reduced Li atomic charge in the complex. Another distinction between the H and Li bonds relates to the destination of charge transferred from the NH3 subunit which accumulates on Cl in the former case but on Li in the latter.