Dissecting the THz spectrum of liquid water from first principles via correlations in time and space

Matthias Heyden, Jian Sun, Stefan Funkner, Gerald Mathias, Harald Forbert, Martina Havenith, Dominik Marx

Research output: Contribution to journalArticlepeer-review

349 Scopus citations


Solvation of molecules in water is at the heart of a myriad of molecular phenomena and of crucial importance to understanding such diverse issues as chemical reactivity or biomolecular function. Complementing well-established approaches, it has been shown that laser spectroscopy in the THz frequency domain offers new insights into hydration from small solutes to proteins. Upon introducing spatially-resolved analyses of the absorption cross section by simulations, the sensitivity of THz spectroscopy is traced back to characteristic distance-dependent modulations of absorption intensities for bulk water. The prominent peak at ≈200 cm-1 is dominated by first-shell dynamics, whereas a concerted motion involving the second solvation shell contributes most significantly to the absorption at about 80 cm -1 ≈2.4 THz. The latter can be understood in terms of an umbrella-like motion of two hydrogen-bonded tetrahedra along the connecting hydrogen bond axis. Thus, a modification of the hydrogen bond network, e.g., due to the presence of a solute, is expected to affect vibrational motion and THz absorption intensity at least on a length scale that corresponds to two layers of solvating water molecules. This result provides a molecular mechanism explaining the experimentally determined sensitivity of absorption changes in the THz domain in terms of distinct, solute-induced dynamical properties in solvation shells of (bio)molecules - even in the absence of well-defined resonances.

Original languageEnglish (US)
Pages (from-to)12068-12073
Number of pages6
JournalProceedings of the National Academy of Sciences of the United States of America
Issue number27
StatePublished - Jul 6 2010
Externally publishedYes


  • Ab initio molecular dynamics
  • Hydrogen-bonding
  • Infrared spectroscopy
  • Solvation
  • Vibrational modes

ASJC Scopus subject areas

  • General


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