Non-monotonic composition dependence of vibrational phase relaxation rate in binary mixtures

Abstract

We present here isothermal-isobaric N-P-T ensemble molecular dynamics simulations of vibrational phase relaxation in a model system to explore the unusual features arising due to concentration fluctuations which are absent in one component systems. The model studied consider strong attractive interaction between the dissimilar species to discourage phase separation. The model reproduces the experimentally observed nonmonotonic, nearly symmetric, composition dependence of the dephasing rate. In addition, several other experimentally observed features, such as the maximum of the frequency modulation correlation time τ_c at mole fraction near 0.5 and the maximum rate enhancement by a factor of about 3 above the pure component value, are also reproduced. The product of mean square frequency modulation [<Δω²(0)>] with τ_c indicates that the present model is in the intermediate regime of inhomogeneous broadening. The nonmonotonic composition χ_A dependence of the dephasing time τ_v is found to be primarily due to the nonmonotonic χ dependence of τ_c, rather than due to a similar dependence in the amplitude of <Δω²(0)>. The probability distribution of Δω shows a markedly non-Gaussian behavior at intermediate composition (χ_A ≈ 0.5). We have also calculated the composition dependence of the viscosity in order to explore the correlation between the composition dependence of viscosity η with that of τ_v and τ_c. It is found that both the correlation time essentially follow the composition dependence of the viscosity. A mode coupling theory is presented to include the effects of composition fluctuations in binary mixture.