Gunnar Karlström

The influence on the short-range packing in dipolar fluids by molecular shape and by additional higher order electrostatic moments has been investigated by molecular dynamic simulations. The dipole polarization was found to decrease as the particles were elongated parallel to the dipole and to increase for elongation perpendicular to the dipole, eventually forming a nematic order. The addition of a quadrupole lead to a reduction of the polarization, and the influence of an axial octupole was weaker and more complex. Both a decrease and an increase of the polarization is possible depending on the relative dipole-dipole and octupole-octupole interaction strengths and the relative direction of the symmetry axes of the moments. These observations were attributed to the different parity of a dipole and a quadrupole and the same parity of a dipole and an axial octupole under reflection. In addition, further insights into the formation of dipole polarization were obtained. Short polar and long equatorial radii and strong dipole-dipole interaction are particle properties that promote a fluid with a high dipole polarization.