Computer simulation study of thermodynamic scaling of dynamics of 2Ca(NO3)2·3KNO3.

Molecular dynamics (MD) simulations of the glass-former 2Ca(NO3)2·3KNO3, CKN, were performed as a function of temperature at pressures 0.1 MPa, 0.5 GPa, 1.0 GPa, and 2.0 GPa. Diffusion coefficient, relaxation time of the intermediate scattering function, and anion reorientational time were obtained as a function of temperature and densitiy ρ. These dynamical properties of CKN scale as ργ/T with a common value γ = 1.8 ± 0.1. The scaling parameter γ is consistent with the exponent of the repulsive part of an effective intermolecular potential for the repulsion between the atoms at shortest distance in the equilibrium structure of liquid CKN, Ca2+, and oxygen atoms of NO3-. Correlation between potential energy and virial is obeyed for the short-range terms of the potential function, but not for the whole potential including coulombic interactions. Decoupling of diffusion coefficient and reorientational relaxation time from relaxation time take place at a given ργ/T value, i.e., breakdown of Stokes-Einstein and Debye-Stokes-Einstein equations result from combined thermal and volume effects. The MD results agree with correlations proposed between long-time relaxation and short-time dynamics, lnτ ∝ 1/<u2>, where the mean square displacement <u2> concerns a time window of 10.0 ps. It has been found that <u2> scales as ργ/T above and below the glass transition temperature, so that thermodynamic scaling of liquid dynamics can be thought as a consequence of theories relating short- and long-time dynamics, and the more fundamental scaling concerns short-time dynamical properties. [ABSTRACT FROM AUTHOR]