Density functional theory (DFT) calculations are performed on a series of double and single proton-transfer reactions to study the variation in polarizations in complexes during the dynamics of proton transfer from one isoenergetic, hydrogen-bonded ground-state structure to the other. The isotropic average polarizability (alpha(av)) shows an interesting single-humped profile with a maxima coinciding with the transition state of the reaction. Similar profiles are also computed at Nd:YaG frequencies. The origin of the maximal polarizability at the transition state is traced to maximal charge separation and large D (donor)-A (acceptor) distances. Maximal polarizability for the transition state suggests an interesting, novel, and less memory extensive computational tool to locate the transition state for hydrogen-transfer reactions in hydrogen-bonded complexes.