Velocity Autocorrelation Function Research Articles

Diffusion in liquid metals is directed by competing collective modes

The self-diffusion process in a dense liquid is influenced by collective particle movements. Extensive molecular dynamics simulations for liquid aluminium and rubidium evidence a crossover in the diffusion coefficient at about 1.4 times the melting temperature Tm, indicating a profound change in the diffusion mechanism. The corresponding velocity autocorrelation functions demonstrate a decrease of the cage effect with a gradual set in of a power-law decay, they celebrate long time tail. This behavior is caused by a competition of density fluctuations near the melting point with vortex-type particle patterns from transverse currents in the hot fluid. The investigation of the velocity autocorrelation function evidences a gradual transition in dynamics with rising temperature. The competition between these two collective particle movements, one hindering and one enhancing the diffusion process, leads to a non-Arrhenius-type behavior of the diffusion coefficient around 1.4Tm, which signals the transition from a dense to a fluidlike liquid dynamics in the potential energy landscape picture. Published by the American Physical Society 2025

Understanding crystallization and amorphization in liquid Ti cooled at different rates: A molecular dynamics simulation study.

Crystallization and amorphization are important processes and different cooling rates cause these transitions. Obtaining pure metals from their molten state is a challenge unless these two are well understood. Here we study both these transitions in liquid Ti using molecular dynamics simulations wherein Ti is modeled with embedded atom potential. At 1bar, Ti crystal is melted and then cooled from 2200 to 300K with cooling rates of 0.1, 1, and 10 K/ps. When cooled at 0.1 and 1 K/ps, molten Ti crystallizes to bcc phase between 1100 and 1000K, and when cooled at 10 K/ps, it amorphizes between these temperatures. From radial distribution functions and Voronoi tessellation, we observe that liquid to bcc transition takes place through short range distorted hcp/bcc-like structures already present in it. Relaxation dynamics is studied using velocity-autocorrelation functions (VACFs), intermediate scattering function, and dynamic structure factor. For all cooling rates, relaxations in VACFs increase with cooling. However, correlations in them are stronger when the system is cooled at 10 K/ps. Relaxation times decrease and increase between 1100 and 1000K for crystallization and amorphization, respectively, thereafter they increase again with further cooling. The dynamic structure factor shows stronger damping in thermal diffusive motion when systems are cooled at 0.1 and 1 K/ps and vibration peaks shift to higher frequencies when crystallization take place. Our findings support Binder's [K. Binder, Proc. Natl. Acad. Sci. U. S. A. 111, 9374 (2014)] argument that if we cool the system faster than the minimum time needed for the liquid to relax, it will amorphize. This also prevents the growth of pre-ordered domains in it to establish long-range order.

The Study of the Molecular Diffusion in Gases and Liquids

The molecular dynamics calculations of the velocity autocorrelation functions and the diffusion coefficients for argon and krypton atoms in argon have been carried out. The data of the molecular dynamics simulations are analyzed to understand the change of the diffusion mechanism with transition from dense gas to liquid. In dense gases, the diffusion mechanism is the same as in rarefied gases, and the temperature dependences of the diffusion coefficient are alike. A new diffusion mechanism appears in liquids. This diffusion mechanism isn’t connected with the jumping motion of the molecules. Probably, it is connected with the motion of the molecules group surrounding a molecule. Then the velocity of the molecule is relaxed with the decreasing of the average velocity of the molecules group. Various structures of the systems within the vapor – liquid phase transition region have been found and investigated. A comparison of the simulation results with the experimental data on diffusion in gaseous and liquid argon yields good agreement.

Transverse clues on the kiloparsec-scale structure of the circumgalactic medium as traced by C IV absorption

The kiloparsec-scale kinematics and density structure of the circumgalactic medium (CGM) is still poorly constrained observationally, which poses a problem for understanding the role of the baryon cycle in galaxy evolution. Here we present VLT/MUSE integral-field spectroscopy (R ≈ 1800) of four giant gravitational arcs exhibiting W0 ≳ 0.2 Å C IV absorption at eight intervening redshifts, zabs ≈ 2.0–2.5. We detected C IV absorption in a total of 222 adjacent and seeing-uncorrelated sight lines whose spectra sample beams of (“de-lensed”) linear size ≈1 kpc. Our data show that (1) absorption velocities cluster at all probed transverse scales, Δr⊥ ≈ 0–15 kpc, depending on system; (2) the (transverse) velocity dispersion never exceeds the mean (line-of-sight) absorption spread; and (3) the (transverse) velocity autocorrelation function does not resolve kinematic patterns at the above spatial scales, but its velocity projection, ξarc(Δv), exhibits a similar shape to the known two-point correlation function toward quasars, ξQSO(Δv). An empirical kinematic model suggests that these results are a natural consequence of wide-beam observations of an unresolved clumpy medium. Our model recovers both the underlying velocity dispersion of the clumps (70–170 km s−1) and the mean number of clumps per unit area (2–13 kpc−2). The latter constrains the projected mean inter-clump distance to within ≈0.3–0.8 kpc, which we argue is a measure of clump size for a near-unity covering fraction. The model is also able to predict ξarc(Δv) from ξQSO(Δv), suggesting that the strong systems that shape ξarc(Δv) and the line-of-sight velocity components that define ξQSO(Δv) trace the same kinematic population. Consequently, the clumps must possess an internal density structure that generates both weak and strong components. We discuss how our interpretation is consistent with previous observations using background galaxies and multiple quasars as well as its implications for the connection between the small-scale kinematic structure of the CGM and galactic-scale accretion and feedback processes.

Nanobubbles in Ultrapure Water Can Self-Propel.

Nanobubbles are sub- micron-sized gas entities that find applications in a wide range of scientific fields. Typically, they are thought to diffuse according to Brownian motion. We report the existence of self-propelled motion of oxygen bulk nanobubbles in ultrapure water at body temperature. Their motion, to a large extent, is self-affine; there are different scaling exponents along the x- and y-axes as well as for the lateral displacement. We use fractal analysis, and we calculate the structure function, the normalised velocity autocorrelation function, the skewness, and the kurtosis. All descriptors attest the existence of a quasi-Gaussian stochastic process, which is classified as fractional Brownian motion. More than 50 % of the trajectories along the x-axis follow superdiffusion, while this amount drops to 30 % for motion along the y-axis as a result of the asymmetry of the field of view.

Human Pluripotent Stem Cell Colony Migration Is Related to Culture Environment and Morphological Phenotype.

Human pluripotent stem cells (hPSCs) are an important tool in the field of regenerative medicine due to their ability to differentiate towards all tissues of the adult organism. An important task in the study of hPSCs is to understand the factors that influence the maintenance of pluripotent and clonal characteristics of colonies represented by their morphological phenotype. Such factors include the ability of colonies to migrate during growth. In this work, we measured and analyzed the migration trajectories of hPSC colonies obtained from bright-field images of three cell lines, including induced hPSC lines AD3 and HPCASRi002-A (CaSR) and human embryonic stem cell line H9. To represent the pluripotent status, the colonies were visually phenotyped into two classes having a "good" or "bad" morphological phenotype. As for the migration characteristics, we calculated the colony speed and distance traveled (mobility measures), meandering index (motion persistence measures), outreach ratio (trajectory tortuosity characteristic), as well as the velocity autocorrelation function. The analysis revealed that the discrimination of phenotypes by the migration characteristics depended on both the cell line and growth environment. In particular, when the mTESR1/Matrigel culture environment was used, "good" AD3 colonies demonstrated a higher average migration speed than the "bad" ones. The reverse relationship between average speeds of "good" and "bad" colonies was found for the H9 line. The CaSR cell line did not show significant differences in the migration speed between the "good" and "bad" phenotypes. We investigated the type of motion exhibited by the colonies by applying two diffusion models to the mean squared displacement dynamics, one model corresponding to normal and the other to anomalous diffusion. The type of diffusion and diffusion parameter values resulting from the model fitting to data demonstrated a similar cell line, environment, and phenotype dependency. Colonies mainly showed a superdiffusive behavior for the mTESR1/Matrigel culture conditions, characterized by longer migration steps compared to the normal random walk. The specific properties of migration features and the patterns of their variation demonstrated in our work can be useful for the development and/or improvement of automated solutions for quality control of hPSCs.

Temperature behavior of the velocity autocorrelation function in large MD models of water.

Velocity autocorrelation functions (VACFs) were calculated using the molecular dynamics method in the TIP4P/2005 and SPC/E water models of 157 464 molecules at temperatures ranging from 250 to 370K. The large size of the models and the high accuracy of the calculations allow us to reliably compute the long-time tails of the VACFs, showing that they systematically change shape from hydrodynamic (argon-like) at high temperatures to that typical of supercooled liquids at low temperatures. These tails in the range of 2-10ps can be well fitted by a combination of two power functions: At-3/2 - Bt-β (A, B > 0, β ≈ 2). It is found that the amplitude of the hydrodynamic asymptote, A, approaches zero as the temperature decreases, thereby rendering the negative power-law decay,-Bt-2, the dominant term within the specified time interval. The presence of a negative -Bt-2 decay in the time interval of 2-10ps determines the specific shape of the VACF long-time tail of water, distinguishing it from ordinary simple liquids. The amplitude B, which is always non-zero, demonstrates a slight increase with rising temperature. At medium temperatures, weak but well-defined damped oscillations are observed on the VACF in the 0.5-2ps interval.

Chemical short-range order increases the phonon heat conductivity in a refractory high-entropy alloy

We study the effects of the chemical short-range order (SRO) on the thermal conductivity of the refractory high-entropy alloy HfNbTaTiZr using atomistic simulation. Samples with different degrees of chemical SRO are prepared by a Monte Carlo scheme. With increasing SRO, a tendency of forming HfTi and TiZr clusters is found. The phonon density of states is determined from the velocity auto-correlation function and chemical SRO modifies the high-frequency part of the phonon density of states. Lattice heat conductivity is calculated by non-equilibrium molecular dynamics simulations. The heat conductivity of the random alloy is lower than that of the segregated binary alloys. Phonon scattering by SRO precipitates might be expected to reduce scattering times and, therefore, decrease thermal conductivity. We find that, in contrast, due to the increase of the conductivity alongside SRO cluster percolation pathways, SRO increases the lattice heat conductivity by around 12 %. This is expected to be a general result, extending to other HEAs.

Extensive study of droplet dynamics with end-grafted polymer chains in Pickering emulsions: Molecular Dynamics simulation and a generic model derived from the generalized Langevin equation

This paper investigates Pickering emulsions (PEs), formed by suspending oil droplets as the dispersed phase in water as the continuous phase using uncharged particles at their interface. To prevent coalescence, the particles are grafted with polymer chains, as emulsifier, not only to provide steric repulsion forces through the excluded volume between monomers floating in water, compensating for the absence of Coulombic repulsive forces but also control emulsion stabilization/destabilization. We combined molecular dynamics (MD) simulations and a generalized Langevin equation (GLE) model to study the dynamics of hairy-droplets using two dynamic quantities: mean square displacement (MSD) and velocity autocorrelation function (VACF). The number of grafted-polymer-chains, f, was the main parameter of interest, while the other parameters of the system were kept constant. A statistical approach was used to estimate theoretical GLE-based model parameters along with their uncertainties, providing insight into the diffusion behavior of these hairy-droplets and specifically addressing the transition between different observed regimes. we capture three specific values of grafted-polymer-chains as, fb=47 and ft=185 describe the transitions of mushroom-brush conformation of grafted-polymer-chains and viscous-viscoelastic behavior of hairy-droplets, respectively, and fg=257 representing the gel-like state number.

The Diffusion Exchange Ratio (DEXR): A minimal sampling of diffusion exchange spectroscopy to probe exchange, restriction, and time-dependence.

Water exchange is increasingly recognized as an important biological process that can affect the study of biological tissue using diffusion MR. Methods to measure exchange, however, remain immature as opposed to those used to characterize restriction, with no consensus on the optimal pulse sequence(s) or signal model(s). In general, the trend has been towards data-intensive fitting of highly parameterized models. We take the opposite approach and show that a judicious sub-sample of diffusion exchange spectroscopy (DEXSY) data can be used to robustly quantify exchange, as well as restriction, in a data-efficient manner. This sampling produces a ratio of two points per mixing time: (i) one point with equal diffusion weighting in both encoding periods, which gives maximal exchange contrast, and (ii) one point with the same total diffusion weighting in just the first encoding period, for normalization. We call this quotient the Diffusion EXchange Ratio (DEXR). Furthermore, we show that it can be used to probe time-dependent diffusion by estimating the velocity autocorrelation function (VACF) over intermediate to long times (~ 2-500 ms). We provide a comprehensive theoretical framework for the design of DEXR experiments in the case of static or constant gradients. Data from Monte Carlo simulations and experiments acquired in fixed and viable ex vivo neonatal mouse spinal cord using a permanent magnet system are presented to test and validate this approach. In viable spinal cord, we report the following apparent parameters from just 6 data points: , , , and , which correspond to the exchange time, restricted or non-Gaussian signal fraction, an effective spherical radius, and permeability, respectively. For the VACF, we report a long-time, power-law scaling with , which is approximately consistent with disordered domains in 3-D. Overall, the DEXR method is shown to be highly efficient, capable of providing valuable quantitative diffusion metrics using minimal MR data.

Two liquid states of distinguishable helium-4: The existence of another non-superfluid frozen by heating.

We show that two liquid states can exist in distinguishable helium-4 (4He) obeying Boltzmann statistics by path integral centroid molecular dynamics (CMD) simulations. This is an indication of quantum liquid polyamorphism induced by the nuclear quantum effect. For 0.08-3.3K and 1-500bar, we extensively conducted the isothermal-isobaric CMD simulations to explore not only possible states and state diagram but also the state characteristics. The distinguishable 4He below 25bar does not freeze down to 0.1K even though it includes no Bosonic exchange effect and, therefore, no Bose condensation. One liquid state, low quantum-dispersion liquid (LQDL), is nearly identical to normal liquid He-I of real 4He. The other is high quantum-dispersion liquid (HQDL) consisting of atoms with longer quantum wavelength. This is another non-superfluid existing below 0.5K or the temperatures of LQDL. The HQDL is also a low-entropy and fragile liquid to exhibit, unlike conventional liquids, rather gas-like relaxation of velocity autocorrelation function, while there the atoms diffuse without noticeable contribution from quantum tunneling. The LQDL-HQDL transition is not a thermodynamic phase transition but a continuous crossover accompanied by the change in the expansion factor of quantum wavelength. Freezing of HQDL into the low quantum-dispersion amorphous solid occurs by heating from 0.2 to 0.3K at 40-50bar, while this P-T condition coincides with the Kim-Chan normal-supersolid phase boundary of real 4He. The obtained state diagram was compared to that of the confined subnano-scale 4He systems, where Bosonic correlation is considerably suppressed.

Structural dynamics of a model of amorphous silicon

We perform extensive simulations and systematic statistical analyses on the structural dynamics of a model of amorphous silicon. The simulations follow the dynamics introduced by Wooten, Winer and Weaire: the energy is obtained with the Keating potential, and the dynamics consists of bond transpositions proposed at random locations and accepted with the Metropolis acceptance ratio. The structural quantities we track are the variations in time of the lateral lengths (Lx, Ly, Lz) of the cuboid simulation cell. We transform these quantities into the volume V and two aspect ratios B1 and B2. Our analysis reveals that at short times, the mean squared displacement (MSD) for all of them exhibits normal diffusion. At longer times, they cross over to anomalous diffusion (AD), with a temperature-dependent anomalous exponent α<1. We analyze our findings in the light of two standard models in statistical physics that feature anomalous dynamics, viz., continuous time random walker (CTRW) and fractional Brownian motion (fBm). We obtain the distribution of waiting times, and find that the data are consistent with a stretched-exponential decay. We also show that the three quantities, V, B1 and B2 exhibit negative velocity autocorrelation functions. These observations together suggest that the dynamics of the material belong to the fBm class.

Orientation time correlation functions up to the fourth cumulant for liquid water

The orientation time correlation functions (OTCFs) of molecular liquids are related to many experimental observations but subtle in theoretical calculations. Usually, the OTCFs at different timescales are described by distinct approaches. The OTCFs at short times were expanded into a series in an order of molecular angular velocity components, and the second cumulant (SC) of the series gave a single-frequency integral over one-mode propagation function weighted by a rotational density of states (DOS) of the liquid, whereas the OTCFs at long times displayed an exponential decay according to the Debye theory. In this paper, we derived the series of the OTCFs up to the fourth cumulant (FC), which gave a sum of twofold frequency integrals over two-mode propagation functions weighted by a product of two rotational DOSs associated with one or two molecular axes. With no need of any fitting parameter, the OTCFs calculated up to the SC and up to the FC were compared with simulation results for liquid water. With the power spectra of angular velocity autocorrelation function, which have a finite value at zero frequency, as the inputs, the OTCFs in both SC and FC schemes resulted in an exponential decay at long times, while the decay times were smaller than the simulation values. The positive results were the calculations with stable rotational instantaneous-normal-mode spectra, which have a linear behavior extrapolated to zero at low frequencies. As the stable rotational INM spectra were used as the inputs, the OTCFs in the SC scheme produced a slow power-law decay, but the OTCFs in the FC scheme captured the simulation behaviors from short to long timescale, including an exponential decay, with the decay times of the 2nd-rank OTCFs close to the simulation values.

Molecular dynamics study of the sonic horizon of microscopic Laval nozzles.

A Laval nozzle can accelerate expanding gas above supersonic velocities, while cooling the gas in the process. This work investigates this process for microscopic Laval nozzles by means of nonequilibrium molecular dynamics simulations of stationary flow, using grand-canonical Monte Carlo particle reservoirs. We study the steady-state expansion of a simple fluid, a monoatomic gas interacting via a Lennard-Jones potential, through an idealized nozzle with atomically smooth walls. We obtain the thermodynamic state variables pressure, density, and temperature but also the Knudsen number, speed of sound, velocity, and the corresponding Mach number of the expanding gas for nozzles of different sizes. We find that the temperature is well defined in the sense that the each velocity components of the particles obey the Maxwell-Boltzmann distribution, but it is anisotropic, especially for small nozzles. The velocity autocorrelation function reveals a tendency towards condensation of the cooled supersonic gas, although the nozzles are too small for the formation of clusters. Overall we find that microscopic nozzles act qualitatively like macroscopic nozzles in that the particles are accelerated to supersonic speeds while their thermal motion relative to the stationary flow is cooled. We find that, like macroscopic Laval nozzles, microscopic nozzles also exhibit a sonic horizon, which is well defined on a microscopic scale. The sonic horizon is positioned only slightly further downstream compared to isentropic expansion through macroscopic nozzles, where it is situated in the most narrow part. We analyze the sonic horizon by studying space-time density correlations, i.e., how thermal fluctuations at two positions of the gas density are correlated in time and find that after the sonic horizon there are indeed no upstream correlations on a microscopic scale.

Energy fluctuations of a Brownian particle freely moving in a liquid

We study the statistical properties of the variation of the kinetic energy of a spherical Brownian particle that freely moves in an incompressible fluid at constant temperature. Based on the underdamped version of the generalized Langevin equation that includes the inertia of both the particle and the displaced fluid, we derive an analytical expression for the probability density function of such a kinetic energy variation during an arbitrary time interval, which exactly amounts to the energy exchanged with the fluid in absence of external forces. We also determine all the moments of this probability distribution, which can be fully expressed in terms of a function that is proportional to the velocity autocorrelation function of the particle. The derived expressions are verified by means of numerical simulations of the stochastic motion of a particle in a viscous liquid with hydrodynamic backflow for representative values of the time-scales of the system. Furthermore, we also investigate the effect of viscoelasticity on the statistics of the kinetic energy variation of the particle, which reveals the existence of three distinct regimes of the energy exchange process depending on the values of the viscoelastic parameters of the fluid.

On the molecular mechanisms of H2/N2 uptake in confined ionic liquids: A computational study

Classical molecular dynamics and hybrid grand canonical Monte Carlo/molecular dynamics simulations were combined to analyze the gas uptake mechanism of hydrogen and nitrogen molecules inside carbon nanotubes filled with an ionic liquid. Several nanotube diameters (from 6 Å to 12.24 Å) and two different ionic liquids (ethylammonium nitrate and 1-ethyl-3-methylimidazolium tetrafluoroborate) were considered to study their effect on the gas capture capacity and on the location of gas molecules within the nanotubes. The simulations showed that nitrogen absorption ability is, in general, greater than that of hydrogen, with the aprotic ionic liquid being more efficient for gas confinement. In addition, gas capture was observed to increase from a scarce 0.4% in bulk ionic liquids up to 8%-25% inside small nanotubes, and the maximum gas uptake was observed for those nanotubes that allow for a greater degree of conformational freedom of the ionic liquid. However, our calculations show that, whereas hydrogen storage is mainly governed by the amount of accessible free volume, for understanding that of nitrogen solvation energetics must be also considered. In all cases, gas molecules are absorbed in the ionic liquid-rich-region, but the interactions with the other components of the system favour their accommodation closer to the carbon wall than to the nanotube centre. Finally, single-particle dynamics of gas molecules was analyzed by means of the velocity autocorrelation functions and the vibrational density of states, which show a blue-shifting when increasing the radius of the nanotube.

Comparative studies of role of different structure factors in various physical properties of some simple liquid metals

In the current work, the comparison of the structure factors and pair correlation functions produced by using eight different theoretical models based on the Perckus-Yevick Hard Sphere (PYHS), Hard Sphere Yukawa (HSY), Mean Spherical Approximation (MSA), Generalized Mean Spherical Approximation (GMSA), Soft Sphere (SS), One-Component Plasma (OCP), Optimized Random Phase Approximation (ORPA) and Charged Hard Sphere (CHS) models for liquid metals viz. Li, Na, K, Rb, Cs, Mg, Zn, Ca, Al, Ga, In, Pb, Sn, Bi and Sb are carried out. Our own model potential is used with the Taylor (TY) screening function in the present computation. With this, certain physical properties such as electrical transport (electrical resistivity), vibrational property (phonon dispersion), dynamical property (velocity autocorrelation function (VACF)) and static (long wavelength of structure factor) properties has also been calculated. When the several theoretical models of the structure factors of the researched simple liquid metals are compared, it is discovered that the experimental data is consistent and in good agreement with the theoretical models.

Microscopic self-dynamics in liquid Ne-D_{2} mixtures: Quantum features and itinerant oscillators reexamined.

In this paper, we report the results of a centroid molecular dynamics (CMD) study of the canonical velocity autocorrelation functions (VACFs) in liquid Ne-D_{2} mixtures at a temperature of T=30K and in the full D_{2}-concentration range (0%≤x_{D_{2}}≤100%). This binary system was selected because of its moderate, although sizable, quantum effects which, as far as its equilibrium properties are concerned, are fully described by the path integral Monte Carlo (PIMC) simulations that have been also implemented. A comprehensive test of the VACF spectral moments carried out using three physical quantities (namely, mean kinetic energy, Einstein frequency, and mean-squared force) obtained from PIMC was performed revealing the potentialities, as well as the limitations, of the CMD approach to the single-particle dynamics in these low-T liquid mixtures. Additional physical information was extracted from the canonical VACFs by fitting their spectra via two distinct methods: the Levesque-Verlet model (LV, very flexible but highly heuristic) and the itinerant oscillator model (IO, based on the physical ground of a single particle rattling inside a short-lived diffusing pseudocage). Both provided good fits of the CMD outputs, with LV being always more adequate than IO in the case of the Ne VACFs, while, as for the D_{2} VACFs, the LV superiority is evident only at high x_{D_{2}} values. However, a peculiar and systematic effect was found after analyzing the IO-fitted parameters: the estimated pseudocage masses turned out to be at least one order of magnitude lower than the corresponding values inferred from the PIMC simulations. This outcome concerns both the Ne and the D_{2} rattling molecule and, as we also discovered, had already been observed (but promptly forgotten) in purely classical simulations of liquid Ar. The possible physical origins of this finding have been finally discussed in some detail, also in connection with the result of the more recent exponential expansion theory (EET), which manages to shed more light on the concept of single particles rattling inside short-lived pseudocages, ultimately demonstrating its untenability.

Molecular simulations of hydrogen diffusion in underground porous media: Implications for storage under varying pressure, confinement, and surface chemistry conditions

Assessing the feasibility of porous formations for hydrogen geo-storage demands a comprehensive understanding of hydrogen (H2) transport behavior in porous media at subsurface conditions. In this study, we employ molecular dynamics simulations to evaluate the effects of pressure (20–500 atm), pore size (2–20 nm), and surface composition on H2 diffusion and interactions within organic and inorganic slit pores. Our analysis of H2 density profiles and interaction energies reveals a distinct preference for H2 molecules to adsorb more readily onto graphene surfaces than kaolinite surfaces. However, self-diffusion results demonstrate that H2 molecules interact relatively weakly with both substrate types. Further insights are provided by velocity autocorrelation functions, emphasizing the occurrence of wall-mediated collisions as H2 molecules diffuse along the pore surfaces, particularly within kaolinite. This highlights the significance of surface roughness in mitigating H2 loss via diffusion in subsurface nanopores, given the small molecular size of H2 and its limited interactions with both organic and inorganic materials. Furthermore, the results demonstrate that self-diffusion coefficients in both pore types increase with pore size and decrease with pressure. Notably, surface composition plays a critical role in low-pressure environments, with self-diffusion coefficients beginning to converge beyond a pressure of 100 atm. Self-diffusion coefficients also become less sensitive to slit aperture beyond a pressure of 50 atm. In high-pressure environments, hydrogen transport is governed by thermal collisions between gas molecules, leading to negligible property variations between pore types. These findings hold significance in the investigation of efficient H2 storage within porous media and caprock formations.

Alkali hydroxide (LiOH, NaOH, KOH) in water: Structural and vibrational properties, including neutron scattering results.

Structural and vibrational properties of aqueous solutions of alkali hydroxides (LiOH, NaOH, and KOH) are computed using quantum molecular dynamics simulations for solute concentrations ranging between 1 and 10M. Element-resolved partial radial distribution functions, neutron and x-ray structure factors, and angular distribution functions are computed for the three hydroxide solutions as a function of concentration. The vibrational spectra and frequency-dependent conductivity are computed from the Fourier transforms of velocity autocorrelation and current autocorrelation functions. Our results for the structure are validated with the available neutron data for 17M concentration of NaOH in water [Semrouni et al., Phys. Chem. Chem. Phys. 21, 6828 (2019)]. We found that the larger ionic radius [rLi+<rNa+<rK+] and higher concentration disturb the hydrogen-bond network of water, resulting in more disordered cationic hydration shell. Our abinitio simulation data for solute concentrations ranging between 1 and 10M can be used to guide future elastic and inelastic neutron-scattering experiments.