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Molecular dynamics simulations of the orientational motion of liquid chloroform at 298 K and 220K

Molecular dynamics simulations of liquid chloroform at 298 K and 220 K, using established optimized potential parameters and run on single-processor workstations, are employed to compute the first- and second-order Legendre polynomial, single-molecule orientational correlation functions describing the tumbling motion of the carbon-hydrogen bond direction. The results of the simulated Raman correlation functions compare well with their experimental counterparts from previously reported Fourier-transformed band contours of two totally symmetric vibration-rotation modes of the liquid. Simulated angular momentum, angular velocity, and intermolecular torque correlation functions are shown, and helped to characterize the insignificance of free orientational mobility within the system. Perturbation effects from rotation-vibration interaction and collision-induced intensities are present, but their effects on the correlation results are not sufficiently high to be of major significance.