Molecular Dynamics Study of Translational and Rotational Diffusion in Liquid Ortho-terphenyl

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 110; no. 1; pp. 13 - 19
• Main Authors: Berry, R. J, Rigby, D, Duan, D, Schwartz, M
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 12.01.2006
• Subjects: Computer Simulation; Diffusion; Magnetic Resonance Spectroscopy - methods; Rotation; Sensitivity and Specificity; Temperature; Terphenyl Compounds - chemistry; Time Factors
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp053797v

NVT molecular dynamics simulations were performed on liquid o-terphenyl as a function of temperature in the range 320−480 K. Computed translational diffusion coefficients displayed the non-Arrhenius behavior expected of a fragile glass-forming liquid and were in good, semiquantitative agreement with experimental results. Rotational correlation functions calculated for various vectors within the molecule exhibited a very short time (0−1 ps) initial decay, followed by a reversal, which corresponds to free reorientation within the “solvent” cage prior to collision with a wall. Rotational correlation times of three orthogonal vectors fixed on the central benzene were close to equal at all temperatures, indicating nearly isotropic overall molecular reorientation. The average correlation times exhibited a non-Arrhenius temperature dependence and were in very good agreement with experimental values derived from 2D and 1H NMR relaxation times. Correlation times of vectors located on the lateral phenyl rings were used to calculate the “spinning” internal rotation diffusion coefficients, which were approximately twice as great as the overall rotational diffusion constants, indicating rapid internal rotation of the phenyl side groups over wide ranges of angle in the liquid.