Feynman path-integral deep potential molecular dynamics (PI-DPMD) calculations have been employed to study both light (H$_2$O) and heavy water (D$_2$O) within the isothermal-isobaric ensemble. In particular, the deep neural network is trained based on ab initio data obtained from the strongly constrained and appropriately normed (SCAN) exchange-correlation functional. Because of the lighter mass of hydrogen than deuteron, the properties of light water is more influenced by nuclear quantum effect than those of heavy water. Clear isotope effects are observed and analyzed in terms of hydrogen-bond structure and electronic properties of water that are closely associated with experimental observables. The molecular structures of both liquid H$_2$O and D$_2$O agree well with the data extracted from scattering experiments. The delicate isotope effects on radial distribution functions and angular distribution functions are well reproduced as well. Our approach demonstrates that deep neural network combined with SCAN functional based ab initio molecular dynamics provides an accurate theoretical tool for modeling water and its isotope effects.
A comprehensive microscopic understanding of ambient liquid water is a major challenge for $ab$ $initio$ simulations as it simultaneously requires an accurate quantum mechanical description of the underlying potential energy surface (PES) as well as extensive sampling of configuration space. Due to the presence of light atoms (e.g., H or D), nuclear quantum fluctuations lead to observable changes in the structural properties of liquid water (e.g., isotope effects), and therefore provide yet another challenge for $ab$ $initio$ approaches. In this work, we demonstrate that the combination of dis…
At room temperature, the quantum contribution to the kinetic energy of a water molecule exceeds the classical contribution by an order of magnitude. The quantum kinetic energy (QKE) of a water molecule is modulated by its local chemical environment and leads to uneven partitioning of isotopes between different phases in thermal equilibrium, which would not occur if the nuclei behaved classically. In this work, we use ab initio path integral simulations to show that QKEs of the water molecules and the equilibrium isotope fractionation ratios of the oxygen and hydrogen isotopes are sensitive pro…
Oxygen Isotope Exchange Between Molten Silicate Spherules and Ambient Water Vapor with Nonzero Relative Velocity: Implication for Chondrule Formation Environment
Nuclear quantum effects, such as zero-point energy and tunneling, cause significant changes to the structure and dynamics of hydrogen bonded systems such as liquid water. However, due to the current inability to simulate liquid water using an exact description of its electronic structure, the interplay between nuclear and electronic quantum effects remains unclear. Here we use simulations that incorporate the quantum mechanical nature of both the nuclei and electrons to provide a fully ab initio determination of the particle quantum kinetic energies, free energy change upon exchanging hydrogen…
Graphene-based laminates, with ultralong and tortuous nanocapillaries formed by simply stacking graphene flakes together, have great promises in filtration and separation. However, the information on liquid water trans-membrane permeation is lacking, which is the most fundamental problem and of crucial importance in solution-based mass transport. Here, based on isotope labelling, we investigate the liquid water transportation through graphene-based nanocapillaries under no external hydrostatic pressures. Liquid water can afford an unimpeded permeation through graphene-based nanochannels with a…
Free energy differences $ΔF:=F-F_{\text{prism}}$ are computed for several isomers of water hexamer relative to the "prism" isomer using the self-consistent phonons method. %$ΔF:=F-F({prism})$ We consider the isotope effect defined by the quantity $δF_{D_2O}:=ΔF_{\rm D_2O}-ΔF_{\rm H_2O}$, and the quantum effect, $δF_{\hbar=0}:=ΔF_{\hbar=0}-ΔF_{\rm H_2O}$, and evaluate them using different flexible water models. While both $δF_{D_2O}$ and $δF_{\hbar=0}$ are found to be rather small for all of the potentials, they are especially small for two of the empirical models, q-TIP4P/F and TTM3-F, compare…
Hydrogen isotope separation has been effectively achieved using gaseous H2/D2 filtered through graphene/Nafion composite membranes. Nevertheless, deuteron nearly does not exist in the form of gaseous D2 in nature but in liquid water. Thus, it is a more feasible way to separate and enrich deuterium from water. Herein we have successfully transferred monolayer graphene to a rigid and porous polymer substrate PITEM (polyimide tracked film), which could avoid the swelling problem of the Nafion substrate, as well as keep the integrity of graphene. Meanwhile, defects in large area of CVD graphene co…
Within the framework of Kohn-Sham density functional theory (DFT), the ability to provide good predictions of water properties by employing a strongly constrained and appropriately normed (SCAN) functional has been extensively demonstrated in recent years. Here, we further advance the modeling of water by building a more accurate model on the fourth rung of Jacob's ladder with the hybrid functional, SCAN0. In particular, we carry out both classical and Feynman path-integral molecular dynamics calculations of water with the SCAN0 functional and the isobaric-isothermal ensemble. In order to gene…
When uranyl nitrate is photolysed in the water solution, light isotope ${}^{235}{\rm U}$ is separated from isotope ${}^{238}{\rm U}$ ; an enrichment factor $K = 1.04$ . The initial samples were depleted by a light isotope of uranium ${}^{235}{\rm U}$ (degree $β= 0.00455$). Regenerated uranyl nitrate was enriched by an isotope of uranium ${}^{235}{\rm U}$ (degree $α= 0.00464$). Uranium tetrafluoride was depleted by an isotope of uranium ${}^{235}{\rm U}$ (degree $β= 0.00446$). Uranium isotopes are separated by the magnetic isotope effect (MIE) in uranyl nitrate photoreduction.
Nuclear quantum effects lead to an anomalous shift of the volume of hexagonal ice; heavy ice has a larger volume than light ice. This anomaly in ice increases with temperature and persists in liquid water up to the boiling point. We study nuclear quantum effects on the density and compressibility of several ice-like structures and crystalline ice phases. By calculating the anisotropic contributions to the stain tensor, we analyze how the compressibility changes along different directions in hexagonal ice, and find that hexagonal ice is softer along the x-y plane than the z-direction. Furthermo…
The isotope effect in the melting temperature of ice Ih has been studied by free energy calculations within the path integral formulation of statistical mechanics. Free energy differences between isotopes are related to the dependence of their kinetic energy on the isotope mass. The water simulations were performed by using the q-TIP4P/F model, a point charge empirical potential that includes molecular flexibility and anharmonicity in the OH stretch of the water molecule. The reported melting temperature at ambient pressure of this model (T = 251 K) increases by 6.5+-0.5 K and 8.2+-0.5 K upon …
We perform ab initio molecular dynamics (AIMD) simulation of liquid water in the canonical ensemble at ambient conditions using the SCAN meta-GGA functional approximation, and carry out systematic comparisons with the results obtained from the GGA-level PBE functional, and Tkatchenko-Scheffler van der Waals (vdW) dispersion correction inclusive PBE functional. We analyze various properties of liquid water including radial distribution functions, oxygen-oxygen-oxygen triplet angular distribution, tetrahedrality, hydrogen bonds, diffusion coefficients, ring statistics, density of states, band ga…
A recent paper by Zeidler et al. (PRL 107, 144501 (2011)) describes a neutron scattering experiment on water in which oxygen isotope substitution is successfully achieved for the first time. Differences between scattering patterns with different oxygen isotopes give a combination of the O-O and O-H (or O-D) structure factors, and the method elegantly minimizes some of the problematic inelasticity effects associated with neutron scattering from hydrogen. Particular conclusions of the new work are that the OH bond length in the light water molecule is about 0.005A longer than the same bond in he…
Predicting the asymmetric structure and dynamics of solvated hydroxide and hydronium in water has been a challenging task from ab initio molecular dynamics (AIMD). The difficulty mainly comes from a lack of accurate and efficient exchange-correlation functional in elucidating the amphiphilic nature and the ubiquitous proton transfer behaviors of the two ions. By adopting the strongly-constrained and appropriately normed (SCAN) meta-GGA functional in AIMD simulations, we systematically examine the amphiphilic properties, the solvation structures, the electronic structures, and the dynamic prope…
Water is of the utmost importance for life and technology. However, a genuinely predictive ab initio model of water has eluded scientists. We demonstrate that a fully ab initio approach, relying on the strongly constrained and appropriately normed (SCAN) density functional, provides such a description of water. SCAN accurately describes the balance among covalent bonds, hydrogen bonds, and van der Waals interactions that dictates the structure and dynamics of liquid water. Notably, SCAN captures the density difference between water and ice I{\it h} at ambient conditions, as well as many import…
Density functional simulations of condensed phase water are typically inaccurate, due to the inaccuracies of approximate functionals. A recent breakthrough showed that the SCAN approximation can yield chemical accuracy for pure water in all its phases, but only when its density is corrected. This is a crucial step toward first-principles biosimulations. However, weak dispersion forces are ubiquitous and play a key role in noncovalent interactions among biomolecules, but are not included in the new approach. Moreover, naïve inclusion of dispersion in HF-SCAN ruins its high accuracy for pure wat…
An accurate ab initio theory of the H-bond structure of liquid water requires a high-level exchange correlation approximation from density functional theory. Based on the liquid structures modeled by ab initio molecular dynamics by using maximally localized Wannier functions as a basis, we study the infrared spectrum of water within the canonical ensemble. In particular, we employ both the Perdew-Burke-Ernzerhof (PBE) functional within the generalized gradient approximation (GGA) and the state-of-the-art meta-GGA level approximation provided by the strongly constrained and appropriately normed…
Ice Ih has been studied by path-integral molecular dynamics simulations, using the effective q-TIP4P/F potential model for flexible water. This has allowed us to analyze finite-temperature quantum effects in this solid phase from 25 to 300 K at ambient pressure. Among these effects we find a negative thermal expansion of ice at low temperatures, which does not appear in classical molecular dynamics simulations. The compressibility derived from volume fluctuations gives results in line with experimental data. We have analyzed isotope effects in ice Ih by considering normal, heavy, and tritiated…
When two phases of water are at equilibrium, the ratio of hydrogen isotopes in each is slightly altered due to their different phase affinities. This isotopic fractionation process can be utilized to analyze water's movement in the world's climate. Here we show that equilibrium fractionation ratios, an entirely quantum mechanical property, also provide a sensitive probe to assess the magnitude of nuclear quantum fluctuations in water. By comparing the predictions of a series of water models, we show that those describing the OH chemical bond as rigid or harmonic greatly over-predict the magnit…
The reliability of the recently proposed natural orbital functional supplemented with second-order Møller-Plesset calculations, (NOF-MP2), has been assessed for the mechanistic studies of elementary reactions of transition metal compounds by investigating the dehydrogenation of water by the scandium cation. Both high- and low-spin state potential energy surfaces have been searched thoroughly. Special attention has been paid to the assessment of the capability of the NOF-MP2 method to describe the strong, both static and dynamic, electron correlation effects on the reactivity of Sc+(3D,1D) with…
The Diffusion Monte Carlo (DMC) method is applied to the water monomer, dimer, and hexamer, using q-TIP4P/F, one of the most simple, empirical water models with flexible monomers. The bias in the time step ($Δτ$) and population size ($N_w$) is investigated. For the binding energies, the bias in $Δτ$ cancels nearly completely, while a noticeable bias in $N_w$ still remains. However, for the isotope shift, (e.g, in the dimer binding energies between (H$_2$O)$_2$ and (D$_2$O)$_2$) the systematic errors in $N_w$ do cancel. Consequently, very accurate results for the latter (within $\sim 0.01$ kcal…
Isotopic Fingerprints of Proton-mediated Dielectric Relaxation in Solid and Liquid Water
Austrian Institute of Technology（奥地利技术研究所）；Israel Institute of Technology（以色列理工学院）；University of Washington（华盛顿大学）；École Polytechnique Fédérale de Lausanne（洛桑联邦理工学院）；Hamburg University of Technology（汉堡工业大学）
A longstanding question in water research is the possibility that supercooled liquid water can undergo a liquid-liquid phase transition (LLT) into high- and low-density liquids. We used several complementary molecular simulation techniques to evaluate the possibility of an LLT in an ab initio neural network model of water trained on density functional theory calculations with the SCAN exchange correlation functional. We conclusively show the existence of a first-order LLT and an associated critical point in the SCAN description of water, representing the first definitive computational evidence…
The shift in chemical equilibria due to isotope substitution is often exploited to gain insight into a wide variety of chemical and physical processes. It is a purely quantum mechanical effect, which can be computed exactly using simulations based on the path integral formalism. Here we discuss how these techniques can be made dramatically more efficient, and how they ultimately outperform quasi-harmonic approximations to treat quantum liquids not only in terms of accuracy, but also in terms of computational efficiency. To achieve this goal we introduce path integral quantum mechanics estimato…
Assessment of First-Principles Methods in Modeling the Melting Properties of Water
Princeton University（普林斯顿大学）；Eastern Institute of Technology（东方理工学院）；CIC nanoGUNE BRTA（nanoGUNE应用研究中心）；Ikerbasque, Basque Foundation for Science（伊克尔巴斯科克，巴斯克科学基金会）
Accurate description of the excess charge in water cluster anions is challenging for standard semi-local and (global) hybrid density functional approximations (DFAs). Using the recent unitary invariant implementation of the Perdew-Zunger self-interaction correction (SIC) method using Fermi-Löwdin orbitals, we assess the effect of self-interaction error on the vertical detachment energies of water clusters anions with the local spin density approximation (LSDA), Perdew-Burke-Ernzerhof (PBE) generalized gradient approximation, and the strongly constrained and appropriately normed (SCAN) meta-GGA…
Carrier envelope phase (CEP) stabilized pulses of intense 800 nm light of 5 fs duration are used to probe the dissociation dynamics of dications of isotopically-substituted water, HOD. HOD$^{2+}$ dissociates into either H$^+$ + OD$^+$ or D$^+$ + OH$^+$. The branching ratio for these two channels is CEP-dependent; the OD$^+$/OH$^+$ ratio (relative to that measured with CEP-unstabilized pulses) varies from 150% to over 300% at different CEP values, opening prospects of isotope-dependent control over molecular bond breakage. The kinetic energy released as HOD$^{2+}$ Coulomb explodes is also CEP-d…
Polymer coatings on cellulosic fibres are widely used to enhance the natural fibre properties by improving, for example, the hydrophobicity and wet strength. Here, we investigate the effects of a terpolymer P(S-co-MABP-co-PyMA) coating on cotton linters and eucalyptus fibres to improve the resistance of cellulose fibres against wetness. Coated and uncoated fibres were characterised by using scanning electron microscopy, contact angle measurements, Raman spectroscopy and atomic force microscopy with the objective of correlating macroscopic properties such as the hydrophobicity of the fleece wit…
We studied the effect of self-interaction error (SIE) on the static dipole polarizabilities of water clusters modelled with three increasingly sophisticated, non-empirical density functional approximations (DFAs), viz. the local spin density approximation (LDA), the Perdew-Burke-Ernzherof (PBE) generalized-gradient approximation (GGA), and the strongly constrained and appropriately normed (SCAN) meta-GGA, using the Perdew-Zunger self-interaction-correction (PZ-SIC) energy functional in the Fermi-Löwdin orbital SIC (FLO-SIC) framework. Our results show that while all three DFAs overestimate the…
Scanning probe microscopy (SPM) has been extensively applied to probe interfacial water in many interdisciplinary fields but the disturbance of the probes on the hydrogen-bonding structure of water has remained an intractable problem. Here we report submolecular-resolution imaging of the water clusters on a NaCl(001) surface within the nearly non-invasive region by a qPlus-based noncontact atomic force microscopy. Comparison with theoretical simulations reveals that the key lies in probing the weak high-order electrostatic force between the quadrupole-like CO-terminated tip and the polar water…
Sets of systematic laboratory experiments are presented -- combining Ultra High Vacuum cryogenic and plasma-line deposition techniques -- that allow us to compare H/D isotopic effects in the reaction of H2O (D2O) ice with the hydroxyl radical OD (OH). The latter is known to play a key role as intermediate species in the solid-state formation of water on icy grains in space. The main finding of our work is that the reaction H2O + OD --> OH + HDO occurs and that this may affect the HDO/H2O abundances in space. The opposite reaction D2O + OH --> OD + HDO is much less effective, and also given the…
One striking anomaly of water ice has been largely neglected and never explained. Replacing hydrogen ($^1$H) by deuterium ($^2$H) causes ice to expand, whereas the "normal" isotope effect is volume contraction with increased mass. Furthermore, the anomaly increases with temperature $T$, even though a normal isotope shift should decrease with $T$ and vanish when $T$ is high enough to use classical nuclear motions. In this study, we show that these effects are very well described by {\it ab initio} density functional theory. Our theoretical modeling explains these anomalies, and allows us to pre…
The effect of the applied trajectory length on the convergence of the static dielectric constant and the self-diffusion coefficient were examined for the SPC/E water model in the NVT ensemble with different system size at 293 K. Very long simulation times of 6-8 ns were employed in order to track the convergence of these properties. Temperature dependence and isotope effects, via using D$_2$O instead of H$_2$O, were also investigated. A simulation for the polarizable SWM4-DP model was also carried out to compare the effect of different potential models. Radial distribution functions and the ne…
