Structure and dynamics of water dangling OH bonds in hydrophobic hydration shells. Comparison of simulation and experiment

J Phys Chem A. 2011 Jun 16;115(23):6177-83. doi: 10.1021/jp111346s. Epub 2011 Mar 17.


Molecular dynamics and electric field strength simulations are performed in order to quantify the structural, dynamic, and vibrational properties of non-H-bonded (dangling) OH groups in the hydration shell of neopentane, as well as in bulk water. The results are found to be in good agreement with the experimentally observed high-frequency (∼3660 cm(-1)) OH band arising from the hydration shell of neopentanol dissolved in HOD/D(2)O, obtained by analyzing variable concentration Raman spectra using multivariate curve resolution (Raman-MCR). The simulation results further indicate that hydration shell dangling OH groups preferentially point toward the central carbon atom of neopentane to a degree that increases with the lifetime of the dangling OH.

Publication types

  • Comparative Study
  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Hydrophobic and Hydrophilic Interactions
  • Hydroxyl Radical / chemistry*
  • Molecular Dynamics Simulation*
  • Molecular Structure
  • Thermodynamics*
  • Water / chemistry*


  • Water
  • Hydroxyl Radical