A surface-specific isotope effect in mixtures of light and heavy water

Jian Liu, Richard S. Andino, Christina M. Miller, Xin Chen*, David M. Wilkins, Michele Ceriotti, David E. Manolopoulos

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

49 Citations (Scopus)


Isotope fractionation between different phases is a subtle but very important phenomenon that is related to the quantum nature of light nuclei, and that has important consequences for geochemistry, hydrology, and biology. Here we present a joint experimental/theoretical investigation of the differential segregation of hydrogen and deuterium at the liquid/vapor interface of mixtures of light and heavy water. We use both vibrational sum-frequency spectroscopy and path integral molecular dynamics simulations to quantitatively assess this phenomenon. The experimental and theoretical results indicate that the last layer of water molecules at the liquid/vapor interface is enriched in hydrogen. We discuss in detail the extent, the physical origin, and the implications of this surface-specific isotope effect.

Original languageEnglish
Pages (from-to)2944-2951
Number of pages8
JournalJournal of Physical Chemistry C
Issue number6
Publication statusPublished - 14 Feb 2013
Externally publishedYes


  • Molecular Dynamics
  • Nuclear Quantum Effects
  • Path Integrals
  • Water
  • Sum Frequency Spectroscopy

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

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