The dipole moment distribution on water is improved by using large flexibility and large bending angle

Abstract

A highly flexible model of water with fixed charges is used to study properties of water. The bending angle of an isolated molecule is 125^○ that was chosen to match the experimental dipole moment. The geometry of water in the liquid phase is made closer to that of the rigid SPC/E model by decreasing the bending angle spring constant, k _Θ. The new model, called SPCE-FHΘ, is a modified version of the recently proposed SPCE-FH [J. Alejandre, G.A. Chapela, F. Bresme and J.-P. Hansen, J. Chem. Phys. 130, 174505 (2009)] to simulate ionic solutions which includes short ranged interactions on the hydrogen atoms. By increasing angle flexibility it is possible to obtain, in the liquid phase at ambient conditions, bending angles ⟨Θ(HOH)⟩ ∼ 109^○, dipole moment ⟨μ⟩ ∼ 2.5 D and dielectric constant ⟨ε⟩ ∼ 80. The dipole moment distribution at room temperature goes from 1.5 to 3.5 D due to large fluctuations in bending angle and has the same trend found in ab initio simulations of liquid water. The dipole moment profile at the interface of water varies from 1.9 D in the vapour phase to 2.5 D in the liquid region at 400 K. The SPCE-FHΘ gives dipole moment, dielectric constant, coexisting densities and surface tension along the liquid–vapour coexistence line closer to the experimental values than those obtained for the SPC/E force field.

Keywords:

• dipole moment distribution
• water
• angle flexibility

Acknowledgements

We thank R.M. Lynden-Bell for valuable comments and discussions and for the calculation of the tetrahedral parameter of the SPCE-FHΘ water model.