Short-time reorientational processes in molecular fluids
Department of Physics, University of Durham, Science Labs
South Road, Durham DH1 3LE, UK
2 Department of Physics and Astronomy, The University of Edinburgh Edinburgh, EH9 3JZ, Scotland, UK
Accepted: 21 October 1999
We study the dynamics of liquid CS2 in order to explore reorientation and intermolecular interactions in condensed phases at new levels of detail. A combination of ab initio molecular dynamics simulations and high-resolution spontaneous Raman spectroscopy is applied to investigate torques and rotational correlations in molecular CS2. We find excellent agreement between experiment and computer simulation. The reorientational correlation time at is found to be with a RMS torque of for the experiment and for the simulation. Examination of the ab initio torques in the molecules shows that dipoles induced from fluctuations in molecular shape is the main cause of the attractive forces between molecules.
PACS: 33.15.Vb – Correlation times in molecular dynamics / 61.25.Em – Molecular liquids / 71.15.Pd – Molecular dynamics calculations (Car-Parrinello) and other numerical simulations
© EDP Sciences, 2000