1. Self-aggregation and microhydration mechanisms of monoethanolamine: Far-infrared identification of large-amplitude hydrogen bond libration.
- Author
-
Yazdabadi, S. Hafizi, Mihrin, D., Feilberg, K. L., and Larsen, R. Wugt
- Subjects
AMINO group ,CHEMICAL models ,POTENTIAL energy ,NEON ,SPECTROMETRY - Abstract
The strong tendency for self-aggregation together with an intriguing mechanism for the microhydration of monoethanolamine (MEA) have been explored by low-temperature far-infrared cluster spectroscopy in doped neon "quantum" matrices at 4 K complemented by high-level quantum chemical modeling. In addition to the assignment of new mid-infrared perturbed intramolecular transitions, a distinct far-infrared transition is unambiguously assigned to the concerted large-amplitude hydrogen bond librational motion of the MEA homodimer. This observation confirms a global "head-to-head" intermolecular potential energy minimum associated with the formation of a compact doubly intermolecular OH⋯N hydrogen-bonded cyclic structure, where both monomeric intramolecular OH⋯N hydrogen bonds are broken upon complexation. By means of relative mixing ratio dependencies, dedicated annealing procedures, and selective complexation between MEA and isotopic H 2 16 O and H 2 18 O samples, distinct far-infrared transitions associated with large-amplitude intra-molecular hindered OH torsional motion and inter-molecular H
2 O librational (hindered c-type overall rotational) motion of the MEA monohydrate are furthermore assigned unambiguously for the first time. These spectroscopic observations reveal an intriguing metastable conformation, where H2 O acts as a OH⋯O hydrogen bond donor to the hydroxy group instead of the amino group of MEA upon microhydration in the cryogenic neon environment, where the microhydration strengthens the intramolecular OH⋯N hydrogen bond of MEA due to hydrogen bond cooperativity. [ABSTRACT FROM AUTHOR]- Published
- 2024
- Full Text
- View/download PDF