Abstract We perform path-integral molecular dynamics (PIMD), ring-polymer MD (RPMD), and classical MD simulations of H$$_2$$ O and D$$_2$$ O using the q-TIP4P/F water model over a wide range of temperatures and pressures. The density$$\rho (T)$$ , isothermal compressibility$$\kappa _T(T)$$ , and self-diffusion coefficientsD(T) of H$$_2$$ O and D$$_2$$ O are in excellent agreement with available experimental data; the isobaric heat capacity$$C_P(T)$$ 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$$_2$$ O and D$$_2$$ O exhibit a liquid-liquid critical point (LLCP) at low temperatures and positive pressures. The data from PIMD/MD for H$$_2$$ O and D$$_2$$ O 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$$_2$$ O, from PIMD simulations, is located at$$P_c = 167 \pm 9$$ MPa,$$T_c = 159 \pm 6$$ K, and$$\rho _c = 1.02 \pm 0.01$$ g/cm$$^3$$ . Isotope substitution effects are important; the LLCP location in q-TIP4P/F D$$_2$$ O is estimated to be$$P_c = 176 \pm 4$$ MPa,$$T_c = 177 \pm 2$$ K, and$$\rho _c = 1.13 \pm 0.01$$ g/cm$$^3$$ . 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,$$P_c = 203 \pm 4$$ MPa,$$T_c = 175 \pm 2$$ K, and$$\rho _c = 1.03 \pm 0.01$$ g/cm$$^3$$ ). 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$$T_c$$ for D$$_2$$ O and, particularly, H$$_2$$ O suggest that improved water models are needed for the study of supercooled water.
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Local structure elucidation of tungsten-substituted vanadium dioxide (V$$_{1-x}$$W$$_x$$O$$_2$$)
Abstract Initially, vanadium dioxide seems to be an ideal first-order phase transition case study due to its deceptively simple structure and composition, but upon closer inspection there are nuances to the driving mechanism of the metal-insulator transition (MIT) that are still unexplained. In this study, a local structure analysis across a bulk powder tungsten-substitution series is utilized to tease out the nuances of this first-order phase transition. A comparison of the average structure to the local structure using synchrotron x-ray diffraction and total scattering pair-distribution function methods, respectively, is discussed as well as comparison to bright field transmission electron microscopy imaging through a similar temperature-series as the local structure characterization. Extended x-ray absorption fine structure fitting of thin film data across the substitution-series is also presented and compared to bulk. Machine learning technique, non-negative matrix factorization, is applied to analyze the total scattering data. The bulk MIT is probed through magnetic susceptibility as well as differential scanning calorimetry. The findings indicate the local transition temperature ($$T_c$$ ) is less than the average$$T_c$$ supporting the Peierls-Mott MIT mechanism, and demonstrate that in bulk powder and thin-films, increasing tungsten-substitution instigates local V-oxidation through the phase pathway VO$$_2\, \rightarrow$$ V$$_6$$ O$$_{13} \, \rightarrow$$ V$$_2$$ O$$_5$$ .
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- PAR ID:
- 10370508
- Publisher / Repository:
- Nature Publishing Group
- Date Published:
- Journal Name:
- Scientific Reports
- Volume:
- 12
- Issue:
- 1
- ISSN:
- 2045-2322
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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