Terahertz absorption of dilute aqueous solutions

Matthias Heyden, Douglas J. Tobias, Dmitry Matyushov

Research output: Contribution to journalArticle

33 Citations (Scopus)

Abstract

Absorption of terahertz (THz) radiation by aqueous solutions of large solutes reports on the polarization response of their hydration shells. This is because the dipolar relaxation of the solute is dynamically frozen at these frequencies, and most of the solute-induced absorption changes, apart from the expulsion of water, are caused by interfacial water. We propose a model expressing the dipolar response of solutions in terms of a single parameter, the interface dipole moment induced in the interfacial water by electromagnetic radiation. We apply this concept to experimental THz absorption of hydrated sugars, amino acids, and proteins. None of the solutes studied here follow the expectations of dielectric theories, which predict a negative projection of the interface dipole on the external electric field. We find that this prediction is not able to describe the available experimental data, which instead suggests a nearly zero interface dipole for sugars and a more diverse pattern for amino acids. Hydrophobic amino acids, similarly to sugars, give rise to near zero interface dipoles, while strongly hydrophilic ones are best described by a positive projection of the interface dipole on the external field. The sign of the interface dipole is connected to the slope of the absorption coefficient with the solute concentration. A positive slope, implying an increase in the solution polarity relative to water, mirrors results frequently reported for protein solutions. We therefore use molecular dynamics simulations of hydrated glucose and lambda repressor protein to calculate the interface dipole moments of these solutes and the concentration dependence of the THz absorption. The absorption at THz frequencies increases with increasing solute concentration in both cases, implying a higher polarity of the solution compared to bulk water. The structure of the hydration layer, extracted from simulations, is qualitatively similar in both cases, with spatial correlations between the protein and water dipoles extending 4-5 nm into the bulk. The theory makes a testable prediction of the inversion of the positive slope at THz frequencies to a negative slope at lower frequencies of tens to hundreds of GHz.

Original languageEnglish (US)
Article number235103
JournalJournal of Chemical Physics
Volume137
Issue number23
DOIs
StatePublished - Dec 21 2012

Fingerprint

solutes
aqueous solutions
dipoles
Water
Sugars
sugars
water
slopes
proteins
amino acids
Dipole moment
Amino Acids
Hydration
Terahertz Radiation
hydration
polarity
dipole moments
Repressor Proteins
Electromagnetic Radiation
projection

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry
  • Medicine(all)

Cite this

Terahertz absorption of dilute aqueous solutions. / Heyden, Matthias; Tobias, Douglas J.; Matyushov, Dmitry.

In: Journal of Chemical Physics, Vol. 137, No. 23, 235103, 21.12.2012.

Research output: Contribution to journalArticle

Heyden, Matthias ; Tobias, Douglas J. ; Matyushov, Dmitry. / Terahertz absorption of dilute aqueous solutions. In: Journal of Chemical Physics. 2012 ; Vol. 137, No. 23.
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