title: Coupling of translational and rotational motion in chiral liquids in electromagnetic and circularly polarised electric fields.
abstract: Non-equilibrium molecular dynamics simulations of R and S enantiomers of 1,1-chlorofluoroethane, both for pure liquids and racemic mixtures, have been performed at 298 K in the absence and presence of both electromagnetic (e/m) and circularly polarised electric (CP) fields of varying frequency (100-2200 GHz) and intensity (0.025-0.2 V Å(-1) (rms)). Significant non-thermal field effects were noted in the coupling of rotational and translational motion; for instance, in microwave and far-infrared (MW/IR) e/m fields, marked increases in rotational and translational diffusion vis-à-vis the zero-field case took place at 0.025-0.1 V Å(-1) (rms), with a reduction in translational diffusion vis-à-vis the zero-field case above 0.1 V Å(-1) (rms) above 100 GHz. This was due to enhanced direct coupling of rotational motion with the more intense e/m field at the ideal intrinsic rotational coupling frequency (approximately 700 GHz) leading to such rapidly oscillating rotational motion that extent of translational motion was effectively reduced. In the case of CP fields, rotational and translational diffusion was also enhanced for all intensities, particularly at approximately 700 GHz. For both MW/IR and CP fields, non-linear field effects were evident above around 0.1 V Å(-1) (rms) intensity, in terms of enhancements in translational and rotational motion. Simulation of 90-10 mol. % liquid mixtures of a Lennard-Jones solvent with R and S enantiomer-solutes in MW/IR and CP fields led to more limited promotion of rotational and translational diffusion, due primarily to increased frictional effects. For both e/m and CP fields, examination of the laboratory- and inertial-frame auto- and cross-correlation functions of velocity and angular velocity demonstrated the development of explicit coupling with the external fields at the applied frequencies, especially so in the more intense fields where nonlinear effects come into play. For racemic mixtures, elements of the laboratory- and inertial-frame velocity and angular velocity were found to couple with each other to a lesser extent.
authors.affiliation: The SEC Strategic Research Cluster and the Centre for Synthesis and Chemical Biology, School of Chemical and Bioprocess Engineering, University College Dublin, Belfield, Dublin 4, Ireland. niall.english@ucd.ie
authors.forename: Niall J
authors.initials: NJ
authors.lastname: English
authors.forename: Peter G
authors.initials: PG
authors.lastname: Kusalik
authors.forename: Sarah A
authors.initials: SA
authors.lastname: Woods
mesh_terms: D055590:Electromagnetic Phenomena; D056004:Molecular Dynamics Simulation; D013237:Stereoisomerism