Molecular electrostatic properties of ions in an ionic liquid

PRADO C.E.R., DEL POPOLO M.G., YOUNGS T.G.A., KOHANOFF J., LYNDEN-BELL R.M.

MOLECULAR PHYSICS

TAYLOR & FRANCIS LTD

Año: 2006 vol. 104 p. 2477 - 2483

0026-8976

We have analysed the electronic wave functions from an ab initio simulation of the ionic liquid ( room temperature molten salt) dimethyl imidazolium chloride ([dmim][Cl] or [C(1)mim][CI]) using localized Wannier orbitals. This allows us to assign electron density to individual ions. The probability distributions of the ionic dipole moments for an isolated ion and for ions in solution are compared. The liquid environment is found to polarize the cation by about 0.7D and to increase the amplitude of the fluctuations in the dipole moments of both cation and anion. The relative changes in nuclear and electronic contributions are shown. The implications for classical force fields are discussed.