Computer simulation study of rotational diffusion in polar liquids of different types

Abstract

Rotational diffusion in liquid acetonitrile, dimethylsulphoxide (DMSO), water, and methanol is studied with molecular dynamics simulations. The effects of hydrogen bonding and local dipole-dipole correlations (Kirkwood g-factor) on the relationship between the single molecule and collective relaxation are examined. The first rank single molecule dipole moment autocorrelation functions (ACFs) are constructed in the molecule-fixed coordinate frame and the principal components of rotation diffusion tensor are reported. Higher rank orientational ACFs are computed. These ACFs, as a rule, are strongly nonexponential (at least not single exponential) at longer times and the decomposition of these functions into a series of single exponentials results in broad distributions of relaxation times, with the broadening being particularly prominent in the case of higher rank ACFs. The rank dependence of characteristic times calculated as weighted averages over the relaxation time distributions does not follow the pattern of small angle (Debye) diffusion model for all liquids studied in this work except methanol. In contradiction, the same rank dependence computed by direct integration of ACFs leads to good agreement with the Debye diffusion model in the case of acetonitrile, DMSO, and water (but not methanol). The linear-angular momentum cross correlation functions are also computed and the effect of rototranslational coupling on reorientaional relaxation at longer times (>1.0 ps) is found to be small.