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

Tomlinson-Phillips, Jill; Davis, Joel; Ben-Amotz, Dor; Spångberg, Daniel; Pejov, Ljupčo; Hermansson, Kersti

doi:10.1021/jp111346s

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

Journal

The journal of physical chemistry. A

Date Issued

2011-06-16

Author(s)

Tomlinson-Phillips, Jill

Davis, Joel

Ben-Amotz, Dor

Spångberg, Daniel

Pejov, Ljupčo

Hermansson, Kersti

DOI

10.1021/jp111346s

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.