Crossover from hydrogen to chemical bonding

B Dereka, Q Yu, NHC Lewis, WB Carpenter… - Science, 2021 - science.org
Science, 2021science.org
Hydrogen bonds (H-bonds) can be interpreted as a classical electrostatic interaction or as a
covalent chemical bond if the interaction is strong enough. As a result, short strong H-bonds
exist at an intersection between qualitatively different bonding descriptions, with few
experimental methods to understand this dichotomy. The [FHF]− ion represents a bare short
H-bond, whose distinctive vibrational potential in water is revealed with femtosecond two-
dimensional infrared spectroscopy. It shows the superharmonic behavior of the proton …
Hydrogen bonds (H-bonds) can be interpreted as a classical electrostatic interaction or as a covalent chemical bond if the interaction is strong enough. As a result, short strong H-bonds exist at an intersection between qualitatively different bonding descriptions, with few experimental methods to understand this dichotomy. The [F-H-F] ion represents a bare short H-bond, whose distinctive vibrational potential in water is revealed with femtosecond two-dimensional infrared spectroscopy. It shows the superharmonic behavior of the proton motion, which is strongly coupled to the donor-acceptor stretching and disappears on H-bond bending. In combination with high-level quantum-chemical calculations, we demonstrate a distinct crossover in spectroscopic properties from conventional to short strong H-bonds, which identify where hydrogen bonding ends and chemical bonding begins.
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