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Results for “rotational diffusion”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Water dynamics in C–S–H and M-S-H cement pastes: A revised jump-diffusion and rotation-diffusion model

The Quasi-Elastic Neutron Scattering (QENS) spectra from four cement pastes are re-analyzed by a new revised jump-diffusion and rotation-diffusion model (rJRM). From the QENS fit, it can be seen that the rJRM is an improved model to fit QENS spectra within the whole detected neutron energy transfer and scattering vector. By the rJRM fitting, the structure parameters extracted from QENS spectra show that both the additives aluminum-silicate nanotubes (ASN) and carboxyl group functionalized ASN (ASN-COOH) can improve magnesium-silicate-hydrate (M-S-H) toward calcium-silicate-hydrate (C–S–H) direction in mechanical properties, but the improvement is weakened with decreasing temperatures. The extracted dynamical parameters show that there is a dynamic anomaly near 230 K in not only translational but also rotational diffusion of water confined in all the investigated samples. In conclusion, the anomaly in rotational diffusion is new compared with those results obtained by the QENS fit using other models.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Cross-correlation analysis of X-ray photon correlation spectroscopy to extract rotational diffusion coefficients

Coefficients for translational and rotational diffusion characterize the Brownian motion of particles. Emerging X-ray photon correlation spectroscopy (XPCS) experiments probe a broad range of length scales and time scales and are well-suited for investigation of Brownian motion. While methods for estimating the translational diffusion coefficients from XPCS are well-developed, there are no algorithms for measuring the rotational diffusion coefficients based on XPCS, even though the required raw data are accessible from such experiments. In this paper, we propose angular-temporal cross-correlation analysis of XPCS data and show that this information can be used to design a numerical algorithm (Multi-Tiered Estimation for Correlation Spectroscopy [MTECS]) for predicting the rotational diffusion coefficient utilizing the cross-correlation: This approach is applicable to other wavelengths beyond this regime. We verify the accuracy of this algorithmic approach across a range of simulated data.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2024

Multitiered computational methodology for extracting three-dimensional rotational diffusion coefficients from x-ray photon correlation spectroscopy data without structural information

X-ray photon correlation spectroscopy (XPCS) is a powerful technique for analyzing particle systems by investigating their dynamics in suspensions across a broad range of temporal and spatial scales. This is done by illuminating samples with coherent x-ray beams and calculating the correlation function of the obtained x-ray scattering images. XPCS is uniquely suited for studying Brownian dynamics, consisting of translational and rotational diffusion. While traditional XPCS image analysis techniques can extract translational diffusion components, they are unable to estimate rotational diffusion coefficients. Here, we introduce a methodology that combines the angular-temporal cross-correlation analysis and a algorithmic framework called Multi-Tiered Estimation for Correlation Spectroscopy in 3D for estimating three-dimensional rotational diffusion coefficients from XPCS images of three-dimensional particle systems. We demonstrate our methodology for extracting rotational diffusion coefficients from XPCS data by applying it to simulated noisy x-ray images of systems of crossing nanotubes and proteins that evolve under translational and rotational Brownian motion for different diffusion rates. Furthermore, our results show that our approach determines rotational diffusion coefficients within a few percent error.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2024

Multi-Tiered Estimation for Correlation Spectroscopy in 3D (MTECS3D) v0.1

This innovative software estimates rotational diffusion coefficients of particles from X-ray photon correlation spectroscopy (XPCS) data of monodispersed particle systems. It is the first method capable of extracting rotational diffusion information from three-dimensional particle systems using XPCS. Using the angular-temporal cross-correlation of the XPCS images, this software is able to estimate the rotational diffusion coefficients with only a few percent relative errors while requiring minimal prior knowledge of particle structures. This software enhances XPCS analysis capabilities, allowing researchers to study translational and rotational Brownian dynamics of particles in suspension across various temporal and spatial scales.

Hu, Zixi↗
DOE OSTI2020

Stability of a tokamak plasma with diffuse toroidal rotation

The present work considers the stability of a high- $\beta$ , large aspect ratio, circular plasma with diffuse profiles for the safety factor and the angular toroidal frequency (López & Guazzotto, Phys. Plasmas , vol. 24, 032501). An application of the Frieman–Rotenberg formalism results in a system of scalar eigenmode equations whose coupling is retained at the plasma–vacuum transition but is disregarded across the plasma column, which is a standard practice. The solution technique consists of a multidimensional shooting method for the poloidal harmonics; robust initial guesses are constructed by solving the dispersion relation in the static scenario with vanishing magnetic shear. Flow shear appears as a high- $\beta$ toroidal contribution, and we illustrate its destabilizing influence on $n=1$ external kink modes in the presence of ideal and resistive walls. Internal resonances are avoided by means of the selection of appropriate equilibrium parameters. The stabilizing influence of a finite positive average magnetic shear is also exemplified.

Physics↗
DOE OSTI2022

Rotational and translational diffusion of liquid n-hexane: EFP-based molecular dynamics analysis

Molecular Dynamics (MD) simulations based on the Effective Fragment Potential (EFP) method are utilized to provide a comprehensive assessment of diffusion in liquid n-hexane. We decompose translational diffusion into components along and orthogonal to the long axis of the molecule. Rotational diffusion is decomposed into tumbling and spinning motions about this axis. Our analysis yields four corresponding diffusion coefficients which are related to diagonal entries in the complete 6 × 6 diffusion tensor accounting for the three rotational and three translational degrees of freedom and for the potential coupling between them. However, coupling between different degrees of freedom is expected to be minimal for a natural choice of the molecular body-fixed axis, so then off-diagonal entries in the tensor are negligible. This expectation is supported by a hydrodynamic analysis of the diffusion tensor which treats the liquid surrounding the molecule being tracked as a viscous continuum. Thus, the EFP MD analysis provides a comprehensive characterization of diffusion and also reveals expected shortcomings of the hydrodynamic treatment, particularly for rotational diffusion, when applied to neat liquids.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2025

Asymmetric rotations slow down diffusion under confinement

Translation and rotation are the two most fundamental forms of diffusion, yet their coupling mechanism is not clear, especially under confinement. Here, we provided evidence of the coupling between rotation and translation using a substituted benzene molecule as an example. A counterintuitive behavior was observed where the movement of the smaller molecule with an asymmetric shape was unexpectedly slower than the larger one with a symmetric shape in confined channels of zeolite. We showed that this diffusion behavior was caused by the presence of the specific and selective interaction of the asymmetric guest with the pores, which increased the local restricted residence time, thus inhibiting the translation under confinement, as further confirmed by dynamic breakthrough curves, uptake measurements, quasi-elastic neutron scattering, and 2 H solid-state NMR techniques. Our work correlated asymmetric rotation and diffusion under a confined environment, which enriched our understanding of the coupling between rotation and translation and could shed light on a fundamental understanding of the diffusion process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Orientational Pair Correlations and Local Structure of Benzonitrile from Molecular Dynamics Simulations with Comparisons to Experiments [plus supplemental information]

Here, we present an experimentally parametrized molecular dynamics study of single-molecule and collective orientational relaxation in neat benzonitrile through the analysis of the reorientational anisotropy and polarizability anisotropy time-correlation function (PA-TCF). The simulations show that the PA-TCF is dominated by collective reorientation after 20 ps. Collective reorientation is found to be slower than single-molecule reorientation by a factor of 1.67, consistent with recent experiments. The simulations provide direct evidence of local antiparallel benzonitrile configurations. These structures, which have been the center of some debate, are responsible for the slower rate of collective vs. single-molecule reorientation in the liquid. Further structural analysis indicates that significant Coulombic interactions between the nitrile group and hydrogen atoms on adjacent molecules play a role in the formation of the antiparallel structures. The single-molecule dynamics reflected in the anisotropy are complex and consist of a ballistic regime, restricted angular diffusion, and spatially anisotropic free diffusion. The principal components of the rotational diffusion tensor are independently obtained and shown to reproduce the free diffusion regime of the anisotropy for each principal axis according to the predictions of a previous theory.

14 SOLAR ENERGY↗
DOE OSTI2025

Diffusion-mediated passing of molecular species in linear nanopores constrained by orientational alignment

For diffusion-mediated catalytic conversion reactions in materials with narrow linear nanopores, e.g., mesoporous silica MCM-41, a key parameter is the propensity for product species to be able to pass reactant species and thus to efficiently exit the pore. For elongated species, this can require orientational alignment with the pore axis. In this work, we perform benchmark analyses for such solution-phase systems where one of these species is elongated in order to quantify the dependence of this passing propensity, P, on pore diameter and on the rotational diffusion coefficient, Dr, of the elongated species. In particular, we consider the passing of a spherical and an elongated spherocylindrical shaped species in a cylindrical pore in an implicit solvent, where these species cannot overlap. Passing is mediated by diffusive Brownian motion of these species as described by strongly damped Langevin dynamics. We quantify scaling of P for pore width just above the threshold where passing is sterically blocked, and also reveal a significant decrease in P for lower Dr. We also consider the dependence of P on the aspect ratio of the elongated species and obtain an exact result in the limiting regime of large aspect ratio.

Brownian motion↗
DOE OSTI2026

Rotational memory function of SPC/E water

Memory effects are essential for the dynamics of condensed materials and are responsible for non-exponential relaxation of correlation functions of dynamic variables through the memory function. Memory functions of dipole rotations for water have never been calculated directly from molecular dynamics simulations. We present here calculations of memory functions for single-dipole rotations and for the overall dipole moment of the sample for SPC/E water. The normalized memory functions for single-particle and collective dipole dynamics turn out to be nearly identical. This result validates theories of dielectric spectroscopy in terms of single-particle time correlation functions and the connection between the collective and single-particle relaxation times through the Kirkwood factor. The dielectric function in this formalism contains no new dynamic information that does not exist in the single-dipole correlation function. A short memory time, ≲1 fs, justifies the use of the mathematics of rotational diffusion to describe the dynamics of a single molecular dipole moment in bulk water. Here, an analytical equation for the rotational memory time is derived.

Asthagiri, Dilipkumar N. [Oak Ridge National Labor↗
DOE OSTI2022

Dynamics of Glyceline and Interactions of Constituents: A Multitechnique NMR Study

In this work, the dynamics of the organic components of the deep eutectic solvent (DES) glyceline are analyzed using an array of complementary nuclear magnetic resonance (NMR) methods. Fast-Field Cycling 1 H relaxometry, Pulsed Field Gradient diffusion, Nuclear Overhauser Effect Spectroscopy (NOESY), 13 C NMR relaxation and pressure dependent NMR experiments are deployed to sample a range of frequencies and modes of motion of the glycerol and choline components of the DES. Generally, translational and rotational diffusion of glycerol are more rapid than those of choline while short range rotational motions observed from 13 C relaxation indicate slow local motion of glycerol at low choline chloride (ChCl) content. The rates of glycerol and choline local motions become more similar at higher ChCl. This result taken together with pressure dependent NMR studies show that the addition of ChCl makes it easier to disrupt glycerol packing. Finally, a relatively slow hydroxyl H-exchange process between glycerol and choline protons is deduced from the data. Consistent with this, NOESY results indicate relatively little direct H-bonding between glycerol and choline. These results suggest that the glycerol H-bonding network is disrupted as choline is added, but primarily in regions where there is intimate mixing of the two components. Thus, the local dynamics of most of the glycerol, resembles that of pure glycerol until substantial choline chloride is present.

13C NMR relaxation↗
DOE OSTI2026

Langevin and Fokker-Planck analyses for diffusion-mediated passing of circular and discorectangular species in two-dimensional channels

The propensity for pairs of diffusing species to pass each other within narrow channels or pores is of basic interest as a first-passage-type problem. It is also of relevance for solution-phase transport in nanoporous materials, and in particular for catalytic conversion reactions where high yield requires that product species can efficiently pass reactant species to exit the pores. Here, we analyze a two-dimensional model with nonoverlapping circular and discorectangular species confined to a rectangular channel, and where passing is mediated by Brownian dynamics in an implicit solvent. For narrower channels where passing is still possible, the discorectangle must align with the channel to pass the circular species. Behavior of the passing propensity, 𝑃, can be assessed by strongly damped Langevin simulations, or within an equivalent Fokker-Planck equation (FPE) formalism. The latter corresponds to a diffusion problem in a “higher-dimensional channel” with a constriction. We assess the variation of the passing propensity, 𝑃, for a broad range of channel width including its scaling just above the threshold where passing is sterically blocked. Analysis of 𝑃 versus the rotational diffusion coefficient 𝐷 𝑟 of the discorectangle reveals a significant decrease in 𝑃 for lower 𝐷 𝑟 for moderate channel width. This prompts a direct analysis of the regime where 𝐷 𝑟 → 0 , for which the FPE can be reduced to a three-dimensional diffusion problem, precise analysis of which is facilitated by adaptive-mesh finite element methods. The dependence of 𝑃 on the aspect ratio of the discorectangle is also assessed.

Rahman, Md Khaledur [Ames Laboratory (AMES), Ames,↗
DOE OSTI2023

NMR relaxometry characterization of water adsorption in corn stover anatomical fractions

Nuclear magnetic resonance (NMR) relaxometry is applied to provide direct measurement of water adsorption in anatomical fractions of corn stover. NMR transverse T 2 relaxation time distribution measurements indicate multiple water populations, which vary with anatomical fraction and water adsorption. Measured T 2 data are used to calculate thermodynamic properties of Brunauer-Emmet-Teller adsorption theory using a model to estimate mono and bilayer relaxation. T 2 data are used directly to determine rotational diffusion correlation times indicating adsorption interaction strength. T 1 -T 2 longitudinal-transverse relaxation time correlation measurements quantify differences in the molecular level structural order of the adsorbate surface water as a function of water activity, i.e. relative humidity or water vapor partial pressure. The T 1 /T 2 ratio provides a measure of the surface energy related to the adsorption strength and surface diffusive mobility of the water adsorbate and differentiates the anatomical fractions. Furthermore, the results indicate that direct measurement of NMR relaxation times can be used to characterize corn stover biomass water adsorption, data relevant to processing and handling considerations.

09 BIOMASS FUELS↗
DOE OSTI2022

Thermal and concentration effects on 1 H NMR relaxation of Gd 3+ -aqua using MD simulations and measurements

We report gadolinium-based contrast agents are key in clinical MRI for enhancing the longitudinal NMR relativity (r 1 ) of hydrogen nuclei ( 1 H) in water and improving the contrast among different tissues. The importance of MRI in clinical practice cannot be gainsaid, yet the interpretation of MRI relies on models with severe assumptions, reflecting a poor understanding of the molecular-scale relaxation processes. In a step towards building a clearer understanding of the relaxation processes, here we investigate thermal and concentration effects on r 1 of the Gd 3+ -aqua complex using both semi-classical molecular dynamics (MD) simulations and measurements. We follow the MD simulation approach recently introduced by [Singer et al., Phys. Chem. Chem. Phys., 2021, 23, 20974], in which no NMR relaxation model or free-parameter is assumed to predict r 1 , thereby bringing new insights into the physics of r 1 on a molecular scale. We expand the autocorrelation function G(t) in terms of molecular modes and determine the thermal activation energies of the two largest modes, both of which are consistent with the range of literature values for rotational diffusion. We also determine the activation energies for translational diffusion and low-field electron-spin relaxation, both of which are consistent with the literature. Furthermore, we validate the MD simulations at human body temperature and concentrations of the paramagnetic ion used in clinical MRI, and we quantify the uncertainties in both simulations and measurements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Theory and modeling of molecular modes in the NMR relaxation of fluids

Traditional theories of the nuclear magnetic resonance (NMR) autocorrelation function for intra-molecular dipole pairs assume a single-exponential decay, yet the calculated autocorrelation of realistic systems displays a rich, multi-exponential behavior, resulting in anomalous NMR relaxation dispersion (i.e., frequency dependence). We develop an approach to model and interpret the multi-exponential intra-molecular autocorrelation using simple, physical models within a rigorous statistical mechanical development that encompasses both rotational diffusion and translational diffusion in the same framework. Here, we recast the problem of evaluating the autocorrelation in terms of averaging over a diffusion propagator whose evolution is described by a Fokker–Planck equation. The time-independent part admits an eigenfunction expansion, allowing us to write the propagator as a sum over modes. Each mode has a spatial part that depends on the specified eigenfunction and a temporal part that depends on the corresponding eigenvalue (i.e., correlation time) with a simple, exponential decay. The spatial part is a probability distribution of the dipole pair, analogous to the stationary states of a quantum harmonic oscillator. Drawing inspiration from the idea of inherent structures in liquids, we interpret each of the spatial contributions as a specific molecular mode. These modes can be used to model and predict the NMR dipole–dipole relaxation dispersion of fluids by incorporating phenomena on the molecular level. We validate our statistical mechanical description of the distribution in molecular modes with molecular dynamics simulations interpreted without any relaxation models or adjustable parameters: the most important poles in the Padé–Laplace transform of the simulated autocorrelation agree with the eigenvalues predicted by the theory

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Thermal Polymorphism in CsCB11H12

Thermal polymorphism in the alkali-metal salts incorporating the icosohedral monocarba-hydridoborate anion, CB11H12−, results in intriguing dynamical properties leading to superionic conductivity for the lightest alkali-metal analogues, LiCB11H12 and NaCB11H12. As such, these two have been the focus of most recent CB11H12− related studies, with less attention paid to the heavier alkali-metal salts, such as CsCB11H12. Nonetheless, it is of fundamental importance to compare the nature of the structural arrangements and interactions across the entire alkali-metal series. Thermal polymorphism in CsCB11H12 was investigated using a combination of techniques: X-ray powder diffraction; differential scanning calorimetry; Raman, infrared, and neutron spectroscopies; and ab initio calculations. The unexpected temperature-dependent structural behavior of anhydrous CsCB11H12 can be potentially justified assuming the existence of two polymorphs with similar free energies at room temperature: (i) a previously reported, ordered R3 polymorph stabilized upon drying and transforming first to R3c symmetry near 313 K and then to a similarly packed but disordered I43d polymorph near 353 K and (ii) a disordered Fm3 polymorph that initially appears from the disordered I43d polymorph near 513 K along with another disordered high-temperature P63mc polymorph. Quasielastic neutron scattering results indicate that the CB11H12− anions in the disordered phase at 560 K are undergoing isotropic rotational diffusion, with a jump correlation frequency [1.19(9) × 1011 s−1] in line with those for the lighter-metal analogues.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Intrinsic rotation modulation by diffusive neutral particles in tokamaks

Abstract The modulated transport model, a model kinetic ion transport equation for the pedestal and scrape-off layer (SOL), is generalized to self-consistently include effects of a single neutral particle species. The neutrals contribute additional transport terms, modifying the v ∥ -dependent orbit-averaged ion diffusivities of the original work and the resulting predicted intrinsic rotation of the ions. After making simplifying assumptions of the neutral transport, in particular taking the continuous transport limit via a short charge-exchange step expansion, we derive relatively simple analytic expressions that capture the diffusive neutral physics. Within the scope of the model’s validity, the neutral-driven intrinsic rotation can compete with the turbulence-driven intrinsic rotation. However, for physically motivated parameters, the neutral-driven intrinsic rotation appears negligible, either on a term-by-term basis or due to a strong cancellation between the neutral-driven momentum diffusion and pinch terms. It appears that a treatment containing finite charge-exchange steps is necessary to capture neutral transport of strong flow momentum into the confined region from the SOL.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗