HClO4salts ofN,N′-tetramethylalkanes (compounds1–6) and ofN,N′-tetraalkyl-o-xylildiamines (compounds7–11) and HAuCl4salts ofN,N′-tetramethyl-o-xylildiamine-di-N-oxide (compound12) and ofo-xylildipiperidyl-di-N-oxides (compounds13–14) were studied by nmr and ir spectroscopy. It is shown that in the compounds3,4,5, and7–11, long intramolecularhydrogen bonds with large proton polarizability and in compounds12–14, short intramolecularhydrogen bonds with large proton polarizability are formed. The study of the compounds1–6shows that the most favorable conditions for the formation of the intramolecular easily polarizable hydrogen bonds occur with compound4, i.e., if these hydrogen bonds are present in the 7-membered rings. In the case of compounds7–14it is shown that the continua usually observed with easily polarizable hydrogen bonds vanish when these bonds become screened from their solvent environments. Then, instead of continua only bands of the fundamental transitions are observed, with the longbonds in the region 2800–1800 cm−1and with the shortbonds in the region 1200–850 cm−1. This result demonstrates that for the occurrence of the ir continua, the interaction of the easily polarizable hydrogen bonds with their solvent environments is absolutely necessary. Furthermore, it is shown with the long as well as the short hydrogen bonds that the intensity of the continua decreases strongly with deuteration, demonstrating that in both cases the deuteron polarizabilities are much smaller than the proton polarizabilities of the hydrogen or deuterium bonds, respectively. From this observation it is concluded that the proton potentials of these structurally symmetrical hydrogen bonds are considerably deformed by their molecular surroundings.