Journal of Physical Chemistry B, Vol.107, No.35, 9520-9527, 2003
Molecular dynamics study on the glass transition in Ca0.4K0.6(NO3)(1.4)
Molecular dynamics (MD) simulations of the glass-forming liquid Ca0.4K0.6(NO3)(1.4) (CKN) have been performed at several temperatures from a liquid state at 800 K down to a glassy state at 150 K. The well-known Ewald summation method of handling the long-range electrostatic interactions has been replaced by the recently proposed method of truncated shifted Coulomb potential (Wolf; et al. J. Chem. Phys. 1999, 10, 8254). Some comparisons between dynamical properties of liquid CKN simulated with either of these methods are provided. A previously introduced polarizable fluctuating charge model (FCM) for the nitrate anion (Ribeiro, M. C. C. Phys. Rev. B 2000, 61, 3297) has been used. It is shown that the FCM is an improvement on the nonpolarizable rigid ion model (RIM) counterpart as the glass transition temperature T-g of the system simulated with the FCM is in better agreement with the experimental calorimetric value (T-g approximate to 475, 380, and 335 K for the RIM, FCM, and experiment, respectively). Reorientational time correlation functions, P-2(t), are first analyzed as in previous Raman spectroscopy investigations (Jacobsson; et al. J. Non-Cryst. Solids 1994, 172-174, 161), where the reorientational relaxation time, tau(or), was obtained from the short time decay Of P-2(t). Excellent agreement between experimental and calculated tau(or) has been found, including the Arrhenius dependence of tau(or) across tau(g). It is shown, however, that the above analysis of the experimental P-2(t), where only the short time decay is available, is misleading. Contrary to the Raman results, a marked change in activation energy across T-g is obtained when the long time decay of the calculated P-2(t) is considered. The temperature dependence of tau(or) is further compared with the diffusion coefficient, D, and the structural alpha-relaxation time, tau(alpha), obtained from the self-part of the intermediate scattering function. The hierarchy of the decoupling between tau(or), D, and tau(alpha) as CKN is cooled to T-g is shown.