skip to main content

Explore Research Products in the NSF-PAR

  • NSF Public Access
  • Search Results
  • Anomalous properties in the potential energy landscape of a monatomic liquid across the liquid–gas and liquid–liquid phase transitions
Title: Anomalous properties in the potential energy landscape of a monatomic liquid across the liquid–gas and liquid–liquid phase transitions
As a liquid approaches the gas state, the properties of the potential energy landscape (PEL) sampled by the system become anomalous. Specifically, (i) the mechanically stable local minima of the PEL [inherent structures (IS)] can exhibit cavitation above the so-called Sastry volume, v S , before the liquid enters the gas phase. In addition, (ii) the pressure of the liquid at the sampled IS [i.e., the PEL equation of state, P IS ( v)] develops a spinodal-like minimum at v S . We perform molecular dynamics simulations of a monatomic water-like liquid and verify that points (i) and (ii) hold at high temperatures. However, at low temperatures, cavitation in the liquid and the corresponding IS occurs simultaneously and a Sastry volume cannot be defined. Remarkably, at intermediate/high temperatures, the IS of the liquid can exhibit crystallization, i.e., the liquid regularly visits the regions of the PEL that belong to the crystal state. The model liquid considered also exhibits a liquid–liquid phase transition (LLPT) between a low-density and a high-density liquid (LDL and HDL). By studying the behavior of P IS ( v) during the LLPT, we identify a Sastry volume for both LDL and HDL. The HDL Sastry volume marks the onset above which IS are heterogeneous (composed of LDL and HDL particles), analogous to points (i) and (ii) above. However, the relationship between the LDL Sastry volume and the onset of heterogeneous IS is less evident. We conclude by presenting a thermodynamic argument that can explain the behavior of the PEL equation of state P IS ( v) across both the liquid–gas phase transition and LLPT.  more » « less
Award ID(s):
2112550
NSF-PAR ID:
10431075
Author(s) / Creator(s):
; ;
Date Published:
Journal Name:
The Journal of Chemical Physics
Volume:
157
Issue:
12
ISSN:
0021-9606
Page Range / eLocation ID:
124502
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; ( , The Journal of Chemical Physics)
    We perform path integral molecular dynamics (PIMD) simulations of a monatomic liquid that exhibits a liquid–liquid phase transition and liquid–liquid critical point. PIMD simulations are performed using different values of Planck’s constant h, allowing us to study the behavior of the liquid as nuclear quantum effects (NQE, i.e., atoms delocalization) are introduced, from the classical liquid ( h = 0) to increasingly quantum liquids ( h > 0). By combining the PIMD simulations with the ring-polymer molecular dynamics method, we also explore the dynamics of the classical and quantum liquids. We find that (i) the glass transition temperature of the low-density liquid (LDL) is anomalous, i.e., [Formula: see text] decreases upon compression. Instead, (ii) the glass transition temperature of the high-density liquid (HDL) is normal, i.e., [Formula: see text] increases upon compression. (iii) NQE shift both [Formula: see text] and [Formula: see text] toward lower temperatures, but NQE are more pronounced on HDL. We also study the glass behavior of the ring-polymer systems associated with the quantum liquids studied (via the path-integral formulation of statistical mechanics). There are two glass states in all the systems studied, low-density amorphous ice (LDA) and high-density amorphous ice (HDA), which are the glass counterparts of LDL and HDL. In all cases, the pressure-induced LDA–HDA transformation is sharp, reminiscent of a first-order phase transition. In the low-quantum regime, the LDA–HDA transformation is reversible, with identical LDA forms before compression and after decompression. However, in the high-quantum regime, the atoms become more delocalized in the final LDA than in the initial LDA, raising questions on the reversibility of the LDA–HDA transformation. 
    more » « less
  2. ; ; ; ( , Fuel)
    The phase transition from subcritical to supercritical conditions, referred to as transcritical behavior, significantly impacts the evaporation and fuel–air mixing in high-pressure liquid-fuel propulsion systems. Transcritical behavior is characterized as a transition from classical two-phase evaporation to a single-phase gas-like diffusion regime as surface tension and latent heat of vaporization reduce. However, the interfacial behavior represented by the surface tension coefficient and evaporation rate during this transition which are crucial inputs for Computational Fluid Dynamics (CFD) simulations of practical transcritical fuel spray is still missing. This study aims at developing new evaporation rate and surface tension models for transcritical n-dodecane droplets using molecular dynamics (MD) simulations irrespective of the droplet size. As MD simulations are primarily limited to the nanoscale, the new models can bridge the gap between MD and continuum simulations and enable the direct application of these findings to microscopic droplets. A new characteristic timescale, i.e., “undroplet time,” is defined which marks the transition from classical two-phase evaporation to single-phase gas-like diffusion behavior. The undroplet time indicates the onset of droplet core disintegration and penetration of nitrogen molecules into the droplet, which occurs after the vanishment of the surface tension. By normalizing the time with respect to the undroplet time, the rate of surface tension decay, evaporation rate, and the rate of droplet mass depletion become independent of the droplet size. Calculation of pairwise correlation coefficients for the entire MD results shows that both surface tension coefficient and evaporation rate are strongly correlated with the background temperature, while pressure and droplet size play a less significant role past the critical point. Therefore, new models for surface tension coefficient and evaporation rate spanning from sub- to supercritical conditions are developed as a function of background pressure and temperature, which can be used in continuum simulations. The identified phase change behavior based on the undroplet time shows a good agreement with the phase change regime maps obtained using microscale experiments and nanoscale MD predictions. 
    more » « less
  3. ; ; ( , Journal of Heat Transfer)
    null (Ed.)
    Abstract We develop a two-dimensional model for the transient diffusion of gas from the cavities in ridge-type structured surfaces to a quiescent liquid suspended above them in the Cassie state to predict the location of the liquid vapor-interface (meniscus) as a function of time. The transient diffusion equation is numerically solved by a Chebyshev collocation (spectral) method coupled to the Young-Laplace equation and the ideal gas law. We capture the effects of variable meniscus curvature and, subsequently, when applicable, movement of triple contact lines. Results are presented for the evolution of the dissolved gas concentration field in the liquid and, when applicable, the time it takes for a meniscus to depin and that for longevity, i.e., the onset of the Cassie to Wenzel state transition. Two configurations are examined; viz., one where an impermeable membrane pressurizes the liquid above the ridges and one where hydrostatic pressure is considered and the top of the liquid is exposed to non-condensable gas. 
    more » « less
  4. ; ; ( , Scientific Reports)
    Abstract

    We perform path-integral molecular dynamics (PIMD), ring-polymer MD (RPMD), and classical MD simulations of H$$_2$$2O and D$$_2$$2O using the q-TIP4P/F water model over a wide range of temperatures and pressures. The density$$\rho (T)$$ρ(T), isothermal compressibility$$\kappa _T(T)$$κT(T), and self-diffusion coefficientsD(T) of H$$_2$$2O and D$$_2$$2O are in excellent agreement with available experimental data; the isobaric heat capacity$$C_P(T)$$CP(T)obtained from PIMD and MD simulations agree qualitatively well with the experiments. Some of these thermodynamic properties exhibit anomalous maxima upon isobaric cooling, consistent with recent experiments and with the possibility that H$$_2$$2O and D$$_2$$2O exhibit a liquid-liquid critical point (LLCP) at low temperatures and positive pressures. The data from PIMD/MD for H$$_2$$2O and D$$_2$$2O can be fitted remarkably well using the Two-State-Equation-of-State (TSEOS). Using the TSEOS, we estimate that the LLCP for q-TIP4P/F H$$_2$$2O, from PIMD simulations, is located at$$P_c = 167 \pm 9$$Pc=167±9 MPa,$$T_c = 159 \pm 6$$Tc=159±6 K, and$$\rho _c = 1.02 \pm 0.01$$ρc=1.02±0.01 g/cm$$^3$$3. Isotope substitution effects are important; the LLCP location in q-TIP4P/F D$$_2$$2O is estimated to be$$P_c = 176 \pm 4$$Pc=176±4 MPa,$$T_c = 177 \pm 2$$Tc=177±2 K, and$$\rho _c = 1.13 \pm 0.01$$ρc=1.13±0.01 g/cm$$^3$$3. Interestingly, for the water model studied, differences in the LLCP location from PIMD and MD simulations suggest that nuclear quantum effects (i.e., atoms delocalization) play an important role in the thermodynamics of water around the LLCP (from the MD simulations of q-TIP4P/F water,$$P_c = 203 \pm 4$$Pc=203±4 MPa,$$T_c = 175 \pm 2$$Tc=175±2 K, and$$\rho _c = 1.03 \pm 0.01$$ρc=1.03±0.01 g/cm$$^3$$3). Overall, our results strongly support the LLPT scenario to explain water anomalous behavior, independently of the fundamental differences between classical MD and PIMD techniques. The reported values of$$T_c$$Tcfor D$$_2$$2O and, particularly, H$$_2$$2O suggest that improved water models are needed for the study of supercooled water.

     
    more » « less
  5. ; ; ; ; ( , Physical Chemistry Chemical Physics)
    null (Ed.)
    Water + elastin-like polypeptides (ELPs) exhibit a transition temperature below which the chains transform from collapsed to expanded states, reminiscent of the cold denaturation of proteins. This conformational change coincides with liquid–liquid phase separation. A statistical-thermodynamics theory is used to model the fluid-phase behavior of ELPs in aqueous solution and to extrapolate the behavior at ambient conditions over a range of pressures. At low pressures, closed-loop liquid–liquid equilibrium phase behavior is found, which is consistent with that of other hydrogen-bonding solvent + polymer mixtures. At pressures evocative of deep-sea conditions, liquid–liquid immiscibility bounded by two lower critical solution temperatures (LCSTs) is predicted. As pressure is increased further, the system exhibits two separate regions of closed-loop of liquid–liquid equilibrium (LLE). The observation of bimodal LCSTs and two re-entrant LLE regions herald a new type of binary global phase diagram: Type XII. At high-ELP concentrations the predicted phase diagram resembles a protein pressure denaturation diagram; possible “molten-globule”-like states are observed at low concentration. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email