title: Structure and dynamics of water dangling OH bonds in hydrophobic hydration shells. Comparison of simulation and experiment.
abstract: 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.
authors.affiliation: Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, USA.
authors.forename: Jill
authors.initials: J
authors.lastname: Tomlinson-Phillips
authors.forename: Joel
authors.initials: J
authors.lastname: Davis
authors.forename: Dor
authors.initials: D
authors.lastname: Ben-Amotz
authors.forename: Daniel
authors.initials: D
authors.lastname: Spångberg
authors.forename: Ljupčo
authors.initials: L
authors.lastname: Pejov
authors.forename: Kersti
authors.initials: K
authors.lastname: Hermansson
mesh_terms: D057927:Hydrophobic and Hydrophilic Interactions; D017665:Hydroxyl Radical / Q000737:chemistry*; D056004:Molecular Dynamics Simulation; D015394:Molecular Structure; D013816:Thermodynamics; D014867:Water / Q000737:chemistry*
chemical_list: D014867:Water; D017665:Hydroxyl Radical