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In this letter, we examine the virial and the potential energy correlation for the quasi-real model system. This correlation constitutes the framework of the theory of the isomorph in the liquid phase diagram commonly examined using simple-liquids. Interestingly, our results show that for the systems characterized by structural anisotropy and flexible bonds, the instantaneous values of total viral and total potential energy are entirely uncorrelated. It is due to the presence of the intramolecular interactions because the contributions to the virial and potential energy resulting from the intermolecular interactions still exhibit strong linear dependence. Interestingly, in contrast to the results reported for simple-liquids, the slope of the mentioned linear dependence is different than the values of the density scaling exponent. However, our findings show that for the quasi-real materials, the slope of dependence between the virial and potential energy (resulting from the intermolecular interactions) strongly depends on the range of intermolecular distances that are taken into account. Consequently, the value of the slope of the discussed relationship, which enables satisfactory density scaling, can be obtained. Furthermore, we show that the above crucial range of intermolecular distances does not depend on the structure of the system as well as on the thermodynamic conditions.

Theoretical concepts in condensed matter physics are typically verified and also developed by exploiting computer simulations mostly in simple models. Predictions based on these usually isotropic models are often at odds with measurement results obtained for real materials. On the other hand, all-atom simulations are complex and time-consuming. In this paper, we formulate a new strategy for effective molecular modelling, which properly reflects properties of real particles by using quasi-real molecules of simple but anisotropic architecture and identifying the applicable range of intermolecular interactions for a given physical process or quantity. As a demonstration of our method capabilities, we solve an intriguing problem within the density scaling idea that has attracted attention in recent decades due to its hallmarks of universality. It demonstrates that the new strategy for molecular modelling opens broad perspectives for simulation and theoretical research, for example, into unifying concepts in the glass transition physics.

Successful thermodynamic scaling of the structural alpha-relaxation time or transport coefficients of glass-forming liquids determined at various temperatures T and pressures P means the data conform to a single function of the product variable TVgamma, where V is the specific volume and gamma is a material specific constant. In the past two decades we have witnessed successful TVgamma-scaling in many molecular, polymeric, and even metallic glass-formers, and gamma is related to the slope of the repulsive part of the intermolecular potential. The advances made indicate TVgamma-scaling is an important aspect of the dynamic and thermodynamic properties of glass-formers. In this paper we show the origin of TVgamma-scaling is not from the structural alpha-relaxation time. Instead it comes from its precursor, the Johari-Goldstein beta-relaxation or the primitive relaxation of the Coupling Model and their relaxation times or tau_0 respectively. It is remarkable that all relaxation times are functions of TVgamma with the same gama, as well as the fractional exponent of the Kohlrausch correlation function of the structural alpha-relaxation. We arrive at this conclusion convincingly based on corroborative evidences from a number of experiments and molecular dynamics simulations performed on a wide variety of glass-formers and in conjunction with consistency with the predictions of the Coupling Model.

In this Letter, we investigate how changes in the system entropy influence the characteristic time scale of the system molecular dynamics near the glass transition. Independently of any model of thermodynamic evolution of the time scale, against some previous suppositions, we show that the system entropy $S$ is not sufficient to govern the time scale defined by structural relaxation time $\tau $. In the density scaling regime, we argue that the decoupling between $\tau $ and $S$ is a consequence of different values of the scaling exponents $\gamma $ and $\gamma_S $ in the density scaling laws, $\tau = f(\rho ^\gamma /T)$ and $S = h(\rho ^{\gamma_S}/T)$, where $\rho $ and $T$ denote density and temperature, respectively. It implies that the proper relation between $\tau $ and $S$ requires supplementing with a density factor, $u(\rho)$, i.e.,$\tau = g(u(\rho)w(S))$. This meaningful finding additionally demonstrates that the density scaling idea can be successfully used to separate physically relevant contributions to the time scale of molecular dynamics near the glass transition. As an example, we revise the Avramov entropic model of the dependence $\tau (T,\rho)$, giving evidence that its entropic basis has to be extended by the density dependence of the maximal energy barrier for structural relaxation. We also discuss the excess entropy $S_{ex}$, the density scaling of which is found to mimic the density scaling of the total system entropy $S$.

Supercooled liquids are characterized by relaxation times that increase dramatically by cooling or compression. Many liquids have been shown to obey power-law density scaling, according to which the relaxation time is a function of density to some power over temperature. We show that power-law density scaling breaks down for larger density variations than usually studied. This is demonstrated by simulations of the Kob-Andersen binary Lennard-Jones mixture and two molecular models, as well as by experimental results for two van der Waals liquids. A more general form of density scaling is derived, which is consistent with results for all the systems studied. An analytical expression for the scaling function for liquids of particles interacting via generalized Lennard-Jones potentials is derived and shown to agree very well with simulations. This effectively reduces the problem of understanding the viscous slowing down from being a quest for a function of two variables to a search for a single-variable function., Comment: 7 pages, 5 figures

Published dielectric relaxation measurements on polypropylene glycol and 1,4-polyisoprene are analyzed to determine the relative effect that thermal energy and volume have on the temperature dependence of the normal mode relaxation times, and compare this to their effect on the temperature dependence of the local segmental relaxation times. We find that for both polymers at temperatures well above Tg, both relaxation modes are governed more by thermal energy than by volume, although the latter's contribution is not negligible. Such a result is consistent with an assumption underlying models for polymer viscoelasticity, such as the Rouse and tube models, that the friction coefficient governing motions over large length scales can be identified with the local segmental friction coefficient. We also show that relaxation data for both the segmental and the normal mode superimpose, when expressed as a function of the product of the temperature and the volume, the latter raised to a power. This scaling form arises from an inverse power form for the intermolecular potential. The value of the exponent on the volume for these two polymers indicates a relatively "soft" potential., Comment: 15 pages, 3 figures