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Register a new userNonmonotonic dependence of the absolute entropy on temperature in supercooled Stillinger-Weber silicon
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Using a recently developed thermodynamic integration method, we compute the precise values of the excess Gibbs free energy (G^e) of the high density liquid (HDL) phase with respect to the crystalline phase at different temperatures (T) in the supercooled region of the Stillinger-Weber (SW) silicon [F. H. Stillinger and T. A. Weber, Phys. Rev. B. 32, 5262 (1985)]. Based on the slope of G^e with respect to T, we find that the absolute entropy of the HDL phase increases as its enthalpy changes from the equilibrium value at T ge 1065 K to the value corresponding to a non-equilibrium state at 1060 K. We find that the volume distribution in the equilibrium HDL phases become progressively broader as the temperature is reduced to 1060 K, exhibiting van-der-Waals (VDW) loop in the pressure-volume curves. Our results provides insight into the thermodynamic cause of the transition from the HDL phase to the low density phases in SW silicon, observed in earlier studies near 1060 K at zero pressure.
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We study the kinetics of crystallization in deeply supercooled liquid silicon employing computer simulations and the Stillinger-Weber three body potential. The free energy barriers to crystallisation are computed using umbrella sampling Monte Carlo simulations, and for selected low temperature and zero pressure state points, using unconstrained molecular dynamics simulations to reconstruct the free energy from a mean first passage time formulation. We focus on state points that have been described in earlier work [Sastry and Angell, Nature Mater., 2, 739, 2003] as straddling a first order liquid-liquid phase transition (LLPT) between two metastable liquid states. It was argued subsequently [Ricci et al., Mol. Phys., 117, 3254, 2019] that the apparent phase transition is in fact due the loss of metastability of the liquid state with respect to the globally stable crystalline state. The presence or absence of a barrier to crystallization for these state points is therefore of importance to ascertain, with due attention to ambiguities that may arise from the choice of order parameters. We discuss our choice of order parameters and also our choice of methods to calculate the free energy at deep supercooling. We find a well-defined free energy barrier to crystallisation and demonstrate that both umbrella sampling and mean first passage time methods yield results that agree quantitatively. Our results thus provide strong evidence against the possibility that the liquids at state points close to the reported LLPT exhibit slow, spontaneous crystallisation, but they do not address the existence of a LLPT (or lack thereof). We also compute the free energy barriers to crystallisation at other state points over a broad range of temperatures and pressures, and discuss the effect of changes in the microscopic structure of the metastable liquid on the free energy barrier heights.
The supercooled liquid silicon, modeled by Stillinger-Weber potential, shows anomalous increase in heat capacity $C_p$, with a maximum $C_p$ value close to 1060 K at zero pressure. We study equilibration and relaxation of the supercooled SW Si, in the temperature range of 1060 K--1070 K at zero pressure. We find that as the relaxation of the metastable supercooled liquid phase initiates, a straight line region (SLR) is formed in cumulative potential energy distributions. The configurational temperature corresponding to the SLR is close to 1060 K, which was earlier identified as the freezing temperature of 4-coordinated amorphous network. The SLR is found to be tangential to the distribution of the metastable liquid phase and thus influences the broadness of the distribution. As the bath temperature is reduced from 1070 K to 1060 K, the effective temperature approaches the bath temperature which results in broadening of the metastable phase distribution. This, in turn, causes an increase in overall fluctuations of potential energy and hence an increase of heat capacity. We also find that during initial stages of relaxation, 4-coordinated atoms form 6-membered rings with a chair--like structure and other structural units that indicate crystallization. Simultaneously a strong correlation is established between the number of chair-shaped 6-membered rings and the number of 4-coordinated atoms in the system. This shows that all properties related to 4-coordinated particles are highly correlated as the SLR is formed in potential energy distributions and this can be interpreted as a consequence of `freezing of amorphous network formed by 4-coordinated particles.
A novel liquid-liquid phase transition has been proposed and investigated in a wide variety of pure substances recently, including water, silica and silicon. From computer simulations using the Stillinger-Weber classical empirical potential, Sastry and Angell [1] demonstrated a first order liquid-liquid transition in supercooled silicon, subsequently supported by experimental and simulation studies. Here, we report evidence for a liquid-liquid critical end point at negative pressures, from computer simulations using the SW potential. Compressibilities exhibit a growing maximum upon lowering temperature below 1500 K and isotherms exhibit density discontinuities below 1120 K, at negative pressure. Below 1120 K, isotherms obtained from constant volume-temperature simulations exhibit non-monotonic, van der Waals-like behavior signaling a first order transition. We identify Tc ~ 1120 +/- 12 K, Pc -0.60 +/- 0.15 GPa as the critical temperature and pressure for the liquid-liquid critical point. The structure of the liquid changes dramatically upon decreasing the temperature and pressure. Diffusivities vary over 4 orders of magnitude, and exhibit anomalous pressure dependence near the critical point. A strong relationship between local geometry quantified by the coordination number, and diffusivity, is seen, suggesting that atomic mobility in both low and high density liquids can usefully be analyzed in terms of defects in the tetrahedral network structure. We have constructed the phase diagram of supercooled silicon. We identify the lines of compressibility, density extrema (maxima and minima) and the spinodal which reveal the interconnection between thermodynamic anomalies and the phase behaviour of the system as suggested in previous works [2-9]
Numerical simulations and finite-size scaling analysis have been carried out to study the percolation behavior of straight rigid rods of length $k$ ($k$-mers) on two-dimensional square lattices. The $k$-mers, containing $k$ identical units (each one occupying a lattice site), were adsorbed at equilibrium on the lattice. The process was monitored by following the probability $R_{L,k}(theta)$ that a lattice composed of $L times L$ sites percolates at a concentration $theta$ of sites occupied by particles of size $k$. A nonmonotonic size dependence was observed for the percolation threshold, which decreases for small particles sizes, goes through a minimum, and finally asymptotically converges towards a definite value for large segments. This striking behavior has been interpreted as a consequence of the isotropic-nematic phase transition occurring in the system for large values of $k$. Finally, the universality class of the model was found to be the same as for the random percolation model.
Crystallization is a process of great practical relevance in which rare but crucial fluctuations lead to the formation of a solid phase starting from the liquid. Like in all first order first transitions there is an interplay between enthalpy and entropy. Based on this idea, to drive crystallization in molecular simulations, we introduce two collective variables, one enthalpic and the other entropic. Defined in this way, these collective variables do not prejudge the structure the system is going to crystallize into. We show the usefulness of this approach by studying the case of sodium and aluminum that crystallize in the bcc and fcc crystalline structure, respectively. Using these two generic collective variables, we perform variationally enhanced sampling and well tempered metadynamics simulations, and find that the systems transform spontaneously and reversibly between the liquid and the solid phases.
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