Dihydrogen Bonding—Seen through the Eyes of Vibrational Spectroscopy

Abstract

In this work, we analyzed five groups of different dihydrogen bonding interactions and hydrogen clusters with an H (Formula presented.) kernel utilizing the local vibrational mode theory, developed by our group, complemented with the Quantum Theory of Atoms–in–Molecules analysis to assess the strength and nature of the dihydrogen bonds in these systems. We could show that the intrinsic strength of the dihydrogen bonds investigated is primarily related to the protonic bond as opposed to the hydridic bond; thus, this should be the region of focus when designing dihydrogen bonded complexes with a particular strength. We could also show that the popular discussion of the blue/red shifts of dihydrogen bonding based on the normal mode frequencies is hampered from mode–mode coupling and that a blue/red shift discussion based on local mode frequencies is more meaningful. Based on the bond analysis of the H (Formula presented.) (H (Formula presented.)) (Formula presented.) systems, we conclude that the bond strength in these crystal–like structures makes them interesting for potential hydrogen storage applications.