title: Understanding THz spectra of aqueous solutions: glycine in light and heavy water.
abstract: THz spectroscopy of aqueous solutions has been established as of recently to be a valuable and complementary experimental tool to provide direct insights into the solute-solvent coupling due to hydrogen-bond dynamics involving interfacial water. Despite much experimental progress, understanding THz spectra in terms of molecular motions, akin to mid-infrared spectra, still remains elusive. Here, using the osmoprotectant glycine as a showcase, we demonstrate how this can be achieved by combining THz absorption spectroscopy and ab initio molecular dynamics. The experimental THz spectrum is characterized by broad yet clearly discernible peaks. Based on substantial extensions of available mode-specific decomposition schemes, the experimental spectrum can be reproduced by theory and assigned on an essentially quantitative level. This joint effort reveals an unexpectedly clear picture of the individual contributions of molecular motion to the THz absorption spectrum in terms of distinct modes stemming from intramolecular vibrations, rigid-body-like hindered rotational and translational motion, and specific couplings to interfacial water molecules. The assignment is confirmed by the peak shifts observed in the THz spectrum of deuterated glycine in heavy water, which allow us to separate the distinct modes experimentally.
authors.affiliation: Lehrstuhl für Theoretische Chemie and ‡Lehrstuhl für Physikalische Chemie II, Ruhr-Universität Bochum , 44780 Bochum, Germany.
authors.forename: Jian
authors.initials: J
authors.lastname: Sun
authors.forename: Gudrun
authors.initials: G
authors.lastname: Niehues
authors.forename: Harald
authors.initials: H
authors.lastname: Forbert
authors.forename: Dominique
authors.initials: D
authors.lastname: Decka
authors.forename: Gerhard
authors.initials: G
authors.lastname: Schwaab
authors.forename: Dominik
authors.initials: D
authors.lastname: Marx
authors.forename: Martina
authors.initials: M
authors.lastname: Havenith
mesh_terms: D017666:Deuterium Oxide / Q000737:chemistry*; D005998:Glycine / Q000737:chemistry*; D006860:Hydrogen Bonding; D056004:Molecular Dynamics Simulation; D055068:Terahertz Spectroscopy; D014867:Water / Q000737:chemistry*
chemical_list: D014867:Water; D017666:Deuterium Oxide; D005998:Glycine