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1. Potential energy landscape formalism for quantum molecular liquids

   https://doi.org/10.1038/s42004-024-01342-9  

   Eltareb, Ali; Zhou, Yang; Lopez, Gustavo_E; Giovambattista, Nicolas (December 2024, Communications Chemistry)

   Abstract The potential energy landscape (PEL) formalism is a powerful tool within statistical mechanics to study the thermodynamic properties of classical low-temperature liquids and glasses. Recently, the PEL formalism has been extended to liquids/glasses that obey quantum mechanics, but applications have been limited to atomistic model liquids. In this work, we extend the PEL formalism to liquid/glassy water using path-integral molecular dynamics (PIMD) simulations, where nuclear quantum effects (NQE) are included. Our PIMD simulations, based on the q-TIP4P/F water model, show that the PEL of quantum water is both Gaussian and anharmonic. Importantly, the ring-polymers associated to the O/H atoms in the PIMD simulations, collapse at the local minima of the PEL (inherent structures, IS) for both liquid and glassy states. This allows us to calculate, analytically, the IS vibrational density of states (IS-VDOS) of the ring-polymer system using the IS-VDOS of classical water (obtained from classical MD simulations). The role of NQE on the structural properties of liquid/glassy water at various pressures are discussed in detail. Overall, our results demonstrate that the PEL formalism can effectively describe the behavior of molecular liquids at low temperatures and in the glass states, regardless of whether the liquid/glass obeys classical or quantum mechanics. 

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2. Nuclear quantum effects on glassy water under pressure: Vitrification and pressure-induced transformations

   https://doi.org/10.1063/5.0238823  

   Eltareb, Ali; Khan, Bibi A; Lopez, Gustavo E; Giovambattista, Nicolas (December 2024, The Journal of Chemical Physics)

   We perform classical molecular dynamics (MD) and path-integral MD (PIMD) simulations of H2O and D2O using the q-TIP4P/F model over a wide range of temperatures and pressures to study the nuclear quantum effects (NQEs) on (i) the vitrification of liquid water upon isobaric cooling at different pressures and (ii) pressure-induced transformations at constant temperature between low-density amorphous and high-density amorphous ice (LDA and HDA) and hexagonal ice Ih and HDA. Upon isobaric cooling, classical and quantum H2O and D2O vitrify into a continuum of intermediate amorphous ices (IA), with densities in-between those of LDA and HDA (depending on pressure). Importantly, the density of the IA varies considerably if NQEs are included (similar conclusions hold for ice Ih at all pressures studied). While the structure of the IA is not very sensitive to NQE, the geometry of the hydrogen-bond (HB) is. NQE leads to longer and less linear HB in LDA, HDA, and ice Ih than found in the classical case. Interestingly, the delocalization of the H/D atoms is non-negligible and identical in LDA, HDA, and ice Ih at all pressures studied. Our isothermal compression/decompression MD/PIMD simulations show that classical and quantum H2O and D2O all exhibit LDA–HDA and ice Ih-HDA transformations, consistent with experiments. The inclusion of NQE leads to a softer HB-network, which lowers slightly the LDA/ice Ih-to-HDA transformation pressures. Interestingly, the HB in HDA is longer and less linear than in LDA, which is counterintuitive given that HDA is ≈25% denser than LDA. Overall, our results show that, while classical computer simulations provide the correct qualitative phenomenology of ice and glassy water, NQEs are necessary for a quantitative description. 

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3. Evidence of a liquid–liquid phase transition in H$$_2$$O and D$$_2$$O from path-integral molecular dynamics simulations

   https://doi.org/10.1038/s41598-022-09525-x  

   Eltareb, Ali; Lopez, Gustavo E.; Giovambattista, Nicolas (April 2022, Scientific Reports)

   Abstract We perform path-integral molecular dynamics (PIMD), ring-polymer MD (RPMD), and classical MD simulations of H$$_2$$ ${}_2$O and D$$_2$$ ${}_2$O using the q-TIP4P/F water model over a wide range of temperatures and pressures. The density$$\rho (T)$$ $\rho \left(T\right)$, isothermal compressibility$$\kappa _T(T)$$ ${\kappa }_T\left(T\right)$, and self-diffusion coefficientsD(T) of H$$_2$$ ${}_2$O and D$$_2$$ ${}_2$O are in excellent agreement with available experimental data; the isobaric heat capacity$$C_P(T)$$ $C_P\left(T\right)$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$$_2$$ ${}_2$O and D$$_2$$ ${}_2$O exhibit a liquid-liquid critical point (LLCP) at low temperatures and positive pressures. The data from PIMD/MD for H$$_2$$ ${}_2$O and D$$_2$$ ${}_2$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$$_2$$ ${}_2$O, from PIMD simulations, is located at$$P_c = 167 \pm 9$$ $P_c=167\pm 9$ MPa,$$T_c = 159 \pm 6$$ $T_c=159\pm 6$ K, and$$\rho _c = 1.02 \pm 0.01$$ ${\rho }_c=1.02\pm 0.01$ g/cm$$^3$$ ${}^3$. Isotope substitution effects are important; the LLCP location in q-TIP4P/F D$$_2$$ ${}_2$O is estimated to be$$P_c = 176 \pm 4$$ $P_c=176\pm 4$ MPa,$$T_c = 177 \pm 2$$ $T_c=177\pm 2$ K, and$$\rho _c = 1.13 \pm 0.01$$ ${\rho }_c=1.13\pm 0.01$ 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,$$P_c = 203 \pm 4$$ $P_c=203\pm 4$ MPa,$$T_c = 175 \pm 2$$ $T_c=175\pm 2$ K, and$$\rho _c = 1.03 \pm 0.01$$ ${\rho }_c=1.03\pm 0.01$ 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$$T_c$$ $T_c$for D$$_2$$ ${}_2$O and, particularly, H$$_2$$ ${}_2$O suggest that improved water models are needed for the study of supercooled water. 

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4. Molecular-level understanding of the rovibrational spectra of N2O in gaseous, supercritical, and liquid SF6 and Xe

   https://doi.org/10.1063/5.0143395  

   Töpfer, Kai; Koner, Debasish; Erramilli, Shyamsunder; Ziegler, Lawrence_D; Meuwly, Markus (April 2023, The Journal of Chemical Physics)

   The transition between the gas-, supercritical-, and liquid-phase behavior is a fascinating topic, which still lacks molecular-level understanding. Recent ultrafast two-dimensional infrared spectroscopy experiments suggested that the vibrational spectroscopy of N2O embedded in xenon and SF6 as solvents provides an avenue to characterize the transitions between different phases as the concentration (or density) of the solvent increases. The present work demonstrates that classical molecular dynamics (MD) simulations together with accurate interaction potentials allows us to (semi-)quantitatively describe the transition in rotational vibrational infrared spectra from the P-/R-branch line shape for the stretch vibrations of N2O at low solvent densities to the Q-branch-like line shapes at high densities. The results are interpreted within the classical theory of rigid-body rotation in more/less constraining environments at high/low solvent densities or based on phenomenological models for the orientational relaxation of rotational motion. It is concluded that classical MD simulations provide a powerful approach to characterize and interpret the ultrafast motion of solutes in low to high density solvents at a molecular level. 

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5. Solubility Equilibrium Isotope Effects of Noble Gases in Water: Theory and Observations

   https://doi.org/10.1021/acs.jpcb.3c05651  

   Seltzer, Alan M.; Shackleton, Sarah A.; Bourg, Ian C. (November 2023, The Journal of Physical Chemistry B)

   The abundance and isotopic composition of noble gases dissolved in water have many applications in the geosciences. In recent years, new analytical techniques have opened the door to the use of high-precision measurements of noble gas isotopes as tracers for groundwater hydrology, oceanography, mantle geochemistry, and paleoclimatology. These analytical advances have brought about new measurements of solubility equilibrium isotope effects (SEIEs) in water (i.e., the relative solubilities of noble gas isotopes) and their sensitivities to the temperature and salinity. Here, we carry out a suite of classical molecular dynamics (MD) simulations and employ the theoretical method of quantum correction to estimate SEIEs for comparison with experimental observations. We find that classical MD simulations can accurately predict SEIEs for the isotopes of Ar, Kr, and Xe to order 0.01‰, on the scale of analytical uncertainty. However, MD simulations consistently overpredict the SEIEs of Ne and He by up to 40% of observed values. We carry out sensitivity tests at different temperatures, salinities, and pressures and employ different sets of interatomic potential parameters and water models. For all noble gas isotopes, the TIP4P water model is found to reproduce observed SEIEs more accurately than the SPC/E and TIP4P/ice models. Classical MD simulations also accurately capture the sign and approximate magnitude of temperature and salinity sensitivities of SEIEs for heavy noble gases. We find that experimental and modeled SEIEs generally follow an inverse-square mass dependence, which implies that the mean-square force experienced by a noble gas atom within a solvation shell is similar for all noble gases. This inverse-square mass proportionality is nearly exact for Ar, Kr, and Xe isotopes, but He and Ne exhibit a slightly weaker mass dependence. We hypothesize that the apparent dichotomy between He–Ne and Ar–Kr–Xe SEIEs may result from atomic size differences, whereby the smaller noble gases are more likely to spontaneously fit within cavities of water without breaking water–water H-bonds, thereby experiencing softer collisions during translation within a solvation shell. We further speculate that the overprediction of simulated He and Ne SEIEs may result from the neglection of higher-order quantum corrections or the overly stiff representation of van der Waals repulsion by the widely used Lennard-Jones 6–12 potential model. We suggest that new measurements of SEIEs of heavy and light noble gases may represent a novel set of constraints with which to refine hydrophobic solvation theories and optimize the set of interatomic potential models used in MD simulations of water and noble gases. 

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