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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 487 records · Page 27
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Unraveling electronic correlations in warm dense quantum plasmas

The study of matter at extreme densities and temperatures has emerged as a highly active frontier at the interface of plasma physics, material science and quantum chemistry with relevance for planetary modeling and inertial confinement fusion. A particular feature of such warm dense matter is the complex interplay of Coulomb interactions, quantum effects, and thermal excitations, making its rigorous theoretical description challenging. Here, we demonstrate how ab initio path integral Monte Carlo simulations allow us to unravel this intricate interplay for the example of strongly compressed beryllium, focusing on two X-ray Thomson scattering data sets obtained at the National Ignition Facility. We find excellent agreement between simulation and experiment with a very high level of consistency between independent observations without the need for any empirical input parameters. Our results call into question previously used chemical models, with important implications for the interpretation of scattering experiments and radiation hydrodynamics simulations.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2025

Nuclear quantum effects in molecular liquids across chemical space

Abstract Nuclear quantum effects (NQEs) influence many physical and chemical phenomena, particularly those involving light atoms or occurring at low temperatures. However, their impact has been carefully quantified in few systems-like water-and is rarely considered more broadly. Here we use path-integral molecular dynamics to systematically investigate NQEs on thermophysical properties of 92 organic liquids at ambient conditions. Depending on chemical constitution, we find substantial impact across thermal expansivity, compressibility, dielectric constant, enthalpy of vaporization, and notably molar volume, which shows consistent, positive quantum-classical differences up to 5%; similar, less pronounced trends manifest as isotope effects from deuteration. Using data-driven analysis, we identify three features-molar mass, classical hydrogen density, and classical thermal expansivity-that accurately predict NQEs and facilitate understanding of how characteristics like branching and heteroatom content influence behavior. This work highlights the broad relevance of NQEs in molecular liquids, while also providing a conceptual and practical framework to anticipate their impact.

Science & Technology - Other Topics↗
DOE OSTI2024

Deuteration removes quantum dipolar defects from KDP crystals

Abstract Dielectric properties of the hydrogen-bonded ferroelectric crystal KH 2 PO 4 (KDP) differ significantly from those of KD 2 PO 4 (DKDP). It is well established that deuteration affects the interplay of hydrogen-bond switches and heavy ion displacements that underlie the emergence of macroscopic polarization, but a detailed microscopic model is missing. We show that all-atom path integral molecular dynamics simulations can predict the isotope effects, revealing the microscopic mechanism that differentiates KDP and DKDP. Proton tunneling generates phosphate configurations that do not contribute to the polarization. At low temperatures, these quantum dipolar defects are substantial in KDP but negligible in DKDP. These intrinsic defects explain why KDP has lower spontaneous polarization and transition entropy than DKDP. The prominent role of quantum fluctuations in KDP is related to the unusual strength of the hydrogen bonds and should be equally important in other crystals of the KDP family, which exhibit similar isotope effects.

Yang, Bingjia (ORCID:0000000340749553)↗
DOE OSTI2026

Enhancing the efficiency of time-dependent density functional theory calculations of dynamic response properties

X-ray Thomson scattering (XRTS) constitutes an essential technique for diagnosing material properties under extreme conditions, such as high pressures and intense laser heating. Time-dependent density functional theory (TDDFT) is one of the most accurate available ab initio methods for modeling XRTS spectra, as well as a host of other dynamic material properties. However, strong thermal excitations, along with the need to account for variations in temperature and density as well as the finite size of the detector significantly increase the computational cost of TDDFT simulations compared to ambient conditions. In this work, we present a broadly applicable method for optimizing and enhancing the efficiency of TDDFT calculations. Our approach is based on a one-to-one mapping between the dynamic structure factor and the imaginary time density–density correlation function, which naturally emerges in Feynman’s path integral formulation of quantum many-body theory. Specifically, we combine rigorous convergence tests in the imaginary time domain with a constraints-based attenuation of narrow-band fluctuations to improve the efficiency of TDDFT modeling without the introduction of any significant bias. As a result, we can report a speed-up by up to an order of magnitude, thus substantially reducing the burden of computational cost required for XRTS analysis.

Moldabekov, Zhandos A. [Helmholtz-Zentrum Dresden-↗
DOE OSTI2020

Developing new and understanding old approximations in TDDFT

When a system has evolved far from a ground-state, the adiabatic approximations commonly used in time-dependent density functional theory calculations completely fail in some applications, while giving qualitatively good predictions in others, and sometimes even quantitative predictions. It is not clearly understood why this is so, and developing practical approximations going beyond the adiabatic approximation remains a challenge. This paper explores three different lines of investigation. First, an expression for the exact time-dependent exchange–correlation potential suggests that the accuracy of an adiabatic approximation is intimately related to the deviation between the natural orbital occupation numbers of the physical system and those of the Kohn–Sham system, and we explore this on some exactly-solvable model systems. The exact expression further suggests a path to go beyond the adiabatic approximations, and in the second part we discuss a newly proposed class of memory-dependent approximations developed in this way. Finally, we derive a new expression for the exact exchange–correlation potential from a coupling-constant path integration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Polymer escape from a confining potential

The rate of escape of polymers from a two-dimensionally confining potential well has been evaluated using self-avoiding as well as ideal chain representations of varying length, up to 80 beads. Long timescale Langevin trajectories were calculated using the path integral hyperdynamics method to evaluate the escape rate. A minimum is found in the rate for self-avoiding polymers of intermediate length while the escape rate decreases monotonically with polymer length for ideal polymers. The increase in the rate for long, self-avoiding polymers is ascribed to crowding in the potential well which reduces the free energy escape barrier. An effective potential curve obtained using the centroid as an independent variable was evaluated by thermodynamic averaging and Kramers rate theory then applied to estimate the escape rate. While the qualitative features are well reproduced by this approach, it significantly overestimates the rate, especially for the longer polymers. The reason for this is illustrated by constructing a two-dimensional effective energy surface using the radius of gyration as well as the centroid as controlled variables. This shows that the description of a transition state dividing surface using only the centroid fails to confine the system to the region corresponding to the free energy barrier and this problem becomes more pronounced the longer the polymer is. A proper definition of a transition state for polymer escape needs to take into account the shape as well as the location of the polymer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Water dimer equilibrium constant calculation: A quantum formulation including metastable states

We present a full quantum evaluation of the water second virial coefficient B(T) based on the Takahashi-Imada second order approximation. As the associated trace Tr[e{sup −βH{sub A}{sub B}}−e{sup −βH{sub A}{sub B}{sup o}}] is performed in the coordinate representation, it does also include contribution from the whole continuum, i.e., resonances and collision pairs of monomers. This approach is compared to a Path Integral Monte Carlo evaluation of this coefficient by Schenter [J. Chem. Phys. 117, 6573 (2002)] for the TIP4P potential and shown to give extremely close results in the low temperature range (250–450 K) reported. Using a recent ab initio flexible potential for the water dimer, this new formulation leads to very good agreement with experimental values over the whole range of temperatures available. The virial coefficient is then used in the well known relation K{sub p}(T) = −(B(T) − b{sub M})/RT where the excluded volume b{sub M} is assimilated to the second virial coefficient of pure water monomer vapor and approximated from the inner repulsive part of the interaction potential. This definition, which renders b{sub M} temperature dependent, allows us to retrieve the 38 cm{sup 3} mol{sup −1} value commonly used, at room temperature. The resulting values for K{sub p}(T) are in agreement with available experimental data obtained from infrared absorption spectra of water vapor.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Mixed quantum classical calculation of proton transfer reaction rates: From deep tunneling to over the barrier regimes

We present mixed quantum classical calculations of the proton transfer (PT) reaction rates represented by a double well system coupled to a dissipative bath. The rate constants are calculated within the so called nontraditional view of the PT reaction, where the proton motion is quantized and the solvent polarization is used as the reaction coordinate. Quantization of the proton degree of freedom results in a problem of non-adiabatic dynamics. By employing the reactive flux formulation of the rate constant, the initial sampling starts from the transition state defined using the collective reaction coordinate. Dynamics of the collective reaction coordinate is treated classically as over damped diffusive motion, for which the equation of motion can be derived using the path integral, or the mixed quantum classical Liouville equation methods. The calculated mixed quantum classical rate constants agree well with the results from the numerically exact hierarchical equation of motion approach for a broad range of model parameters. Moreover, we are able to obtain contributions from each vibrational state to the total reaction rate, which helps to understand the reaction mechanism from the deep tunneling to over the barrier regimes. The numerical results are also compared with those from existing approximate theories based on calculations of the non-adiabatic transmission coefficients. It is found that the two-surface Landau-Zener formula works well in calculating the transmission coefficients in the deep tunneling regime, where the crossing point between the two lowest vibrational states dominates the total reaction rate. When multiple vibrational levels are involved, including additional crossing points on the free energy surfaces is important to obtain the correct reaction rate using the Landau-Zener formula.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

The Nosé–Hoover looped chain thermostat for low temperature thawed Gaussian wave-packet dynamics

We have used a generalised coherent state resolution of the identity to map the quantum canonical statistical average for a general system onto a phase-space average over the centre and width parameters of a thawed Gaussian wave packet. We also propose an artificial phase-space density that has the same behaviour as the canonical phase-space density in the low-temperature limit, and have constructed a novel Nosé–Hoover looped chain thermostat that generates this density in conjunction with variational thawed Gaussian wave-packet dynamics. This forms a new platform for evaluating statistical properties of quantum condensed-phase systems that has an explicit connection to the time-dependent Schrödinger equation, whilst retaining many of the appealing features of path-integral molecular dynamics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

How to remove the spurious resonances from ring polymer molecular dynamics

Two of the most successful methods that are presently available for simulating the quantum dynamics of condensed phase systems are centroid molecular dynamics (CMD) and ring polymer molecular dynamics (RPMD). Despite their conceptual differences, practical implementations of these methods differ in just two respects: the choice of the Parrinello-Rahman mass matrix and whether or not a thermostat is applied to the internal modes of the ring polymer during the dynamics. Here, we explore a method which is halfway between the two approximations: we keep the path integral bead masses equal to the physical particle masses but attach a Langevin thermostat to the internal modes of the ring polymer during the dynamics. We justify this by showing analytically that the inclusion of an internal mode thermostat does not affect any of the established features of RPMD: thermostatted RPMD is equally valid with respect to everything that has actually been proven about the method as RPMD itself. In particular, because of the choice of bead masses, the resulting method is still optimum in the short-time limit, and the transition state approximation to its reaction rate theory remains closely related to the semiclassical instanton approximation in the deep quantum tunneling regime. In effect, there is a continuous family of methods with these properties, parameterised by the strength of the Langevin friction. Here, we explore numerically how the approximation to quantum dynamics depends on this friction, with a particular emphasis on vibrational spectroscopy. We find that a broad range of frictions approaching optimal damping give similar results, and that these results are immune to both the resonance problem of RPMD and the curvature problem of CMD.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

On the room-temperature phase diagram of high pressure hydrogen: An ab initio molecular dynamics perspective and a diffusion Monte Carlo study

The finite-temperature phase diagram of hydrogen in the region of phase IV and its neighborhood was studied using the ab initio molecular dynamics (MD) and the ab initio path-integral molecular dynamics (PIMD). The electronic structures were analyzed using the density-functional theory (DFT), the random-phase approximation, and the diffusion Monte Carlo (DMC) methods. Taking the state-of-the-art DMC results as benchmark, comparisons of the energy differences between structures generated from the MD and PIMD simulations, with molecular and dissociated hydrogens, respectively, in the weak molecular layers of phase IV, indicate that standard functionals in DFT tend to underestimate the dissociation barrier of the weak molecular layers in this mixed phase. Because of this underestimation, inclusion of the quantum nuclear effects (QNEs) in PIMD using electronic structures generated with these functionals leads to artificially dissociated hydrogen layers in phase IV and an error compensation between the neglect of QNEs and the deficiencies of these functionals in standard ab initio MD simulations exists. This analysis partly rationalizes why earlier ab initio MD simulations complement so well the experimental observations. The temperature and pressure dependencies for the stability of phase IV were also studied in the end and compared with earlier results.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Adding flexibility to the “particles-on-a-sphere” model for large-amplitude motion: POSflex force field for protonated methane

The so-called “particles-on-a-sphere” (POS) model has been introduced a while ago in order to describe in simple terms large-amplitude motion of polyatomic hydrides, XH{sub n}. The POS model of protonated methane, CH{sub 5}{sup +}, has been shown to capture well the essence of the fluxional nature of this enigmatic floppy molecule. Here, we extend this model to the POSflex force field by adding flexibility to the C–H bonds, which are constrained to a common fixed bond length in the original model. This makes the present model extremely efficient for computer simulation, including path integral molecular dynamics in order to assess the crucial quantum effects on nuclear motion at low temperatures. Moreover, the POSflex force field can be conveniently used to study microsolvation effects upon combining it with intermolecular pair potentials to account for solute-solvent interactions. Upon computing static properties as well as thermal and quantum fluctuation effects at ambient and low temperatures, respectively, it is shown that the POSflex model is very well suited to describe the structural properties of bare CH{sub 5}{sup +}, including hydrogen scrambling and thus fluxionality in the first place. The far- to mid-infrared spectrum up to the bending band is roughly described, whereas the model fails to account for the well-structured stretching band by construction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Entropic penalties in circular DNA assembly

The thermodynamic properties of DNA circular molecules are investigated by a new path integral computational method which treats in the real space the fundamental forces stabilizing the molecule. The base pair and stacking contributions to the classical action are evaluated separately by simulating a broad ensemble of twisted conformations. We obtain, for two short sequences, a free energy landscape with multiple wells corresponding to the most convenient values of helical repeat. Our results point to a intrinsic flexibility of the circular structures in which the base pair fluctuations move the system from one well to the next thus causing the local unwinding of the helix. The latter is more pronounced in the shorter sequence whose cyclization causes a higher bending stress. The entropic reductions associated to the formation of the ordered helicoidal structure are estimated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Ice and water droplets on graphite: A comparison of quantum and classical simulations

Ice and water droplets on graphite have been studied by quantum path integral and classical molecular dynamics simulations. The point-charge q-TIP4P/F potential was used to model the interaction between flexible water molecules, while the water-graphite interaction was described by a Lennard-Jones potential previously used to reproduce the macroscopic contact angle of water droplets on graphite. Several energetic and structural properties of water droplets with sizes between 10{sup 2} and 10{sup 3} molecules were analyzed in a temperature interval of 50–350 K. The vibrational density of states of crystalline and amorphous ice drops was correlated to the one of ice Ih to assess the influence of the droplet interface and molecular disorder on the vibrational properties. The average distance of covalent OH bonds is found 0.01 Å larger in the quantum limit than in the classical one. The OO distances are elongated by 0.03 Å in the quantum simulations at 50 K. Bond distance fluctuations are large as a consequence of the zero-point vibrations. The analysis of the H-bond network shows that the liquid droplet is more structured in the classical limit than in the quantum case. The average kinetic and potential energy of the ice and water droplets on graphite has been compared with the values of ice Ih and liquid water as a function of temperature. The droplet kinetic energy shows a temperature dependence similar to the one of liquid water, without apparent discontinuity at temperatures where the droplet is solid. However, the droplet potential energy becomes significantly larger than the one of ice or water at the same temperature. In the quantum limit, the ice droplet is more expanded than in a classical description. Liquid droplets display identical density profiles and liquid-vapor interfaces in the quantum and classical limits. The value of the contact angle is not influenced by quantum effects. Contact angles of droplets decrease as the size of the water droplet increases which implies a positive sign of the line tension of the droplet.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Simultaneous streak and frame interferometry for electron density measurements of laser produced plasmas

A system of two collinear probe beams with different wavelengths and pulse durations was used to capture simultaneously snapshot interferograms and streaked interferograms of laser produced plasmas. The snapshots measured the two dimensional, path-integrated, electron density on a charge-coupled device while the radial temporal evolution of a one dimensional plasma slice was recorded by a streak camera. This dual-probe combination allowed us to select plasmas that were uniform and axisymmetric along the laser direction suitable for retrieving the continuous evolution of the radial electron density of homogeneous plasmas. Demonstration of this double probe system was done by measuring rapidly evolving plasmas on time scales less than 1 ns produced by the interaction of femtosecond, high intensity, laser pulses with argon gas clusters. Experiments aimed at studying homogeneous plasmas from high intensity laser-gas or laser-cluster interaction could benefit from the use of this probing scheme.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2016

Role of temperature on static correlational properties in a spin-polarized electron gas

We have studied the effect of temperature on the static correlational properties of a spin-polarized three-dimensional electron gas (3DEG) over a wide coupling and temperature regime. This problem has been very recently studied by Brown et al. using the restricted path-integral Monte Carlo (RPIMC) technique in the warm-dense regime. To this endeavor, we have used the finite temperature version of the dynamical mean-field theory of Singwi et al, the so-called quantum STLS (qSTLS) approach. The static density structure factor and the static pair-correlation function are calculated, and compared with the RPIMC simulation data. We find an excellent agreement with the simulation at high temperature over a wide coupling range. However, the agreement is seen to somewhat deteriorate with decreasing temperature. The pair-correlation function is found to become small negative for small electron separation. This may be attributed to the inadequacy of the mean-field theory in dealing with the like spin electron correlations in the strong-coupling domain. A nice agreement with RPIMC data at high temperature seems to arise due to weakening of both the exchange and coulomb correlations with rising temperature.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2016

Spin dependent correlations in a homogeneous electron gas at finite temperature

We have studied theoretically the magnetic structure factor of a three-dimensional homogeneous electron gas at finite temperature. The spin density response function has been derived using the Singwi-Tosi-Land-Sjolander (STLS) theory that incorporates the correlation effects through spin anti-symmetric local field correction factor. The numerical results so obtained are compared against the recent path-integral Monte Carlo Simulation data of Brown et al. in the warm-dense regime for various temperature values. We find almost exact agreement at small temperature for different coupling parameter (r{sub s}) values. However, with increasing temperature and decreasing density, there has been observed noticeable disagreement with simulation results. This is attributed to the known failure of the STLS theory in dealing separately with the spin-resolved correlation functions.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2016

Design of geometric phase measurement in EAST Tokamak

The optimum scheme for geometric phase measurement in EAST Tokamak is proposed in this paper. The theoretical values of geometric phase for the probe beams of EAST Polarimeter-Interferometer (POINT) system are calculated by path integration in parameter space. Meanwhile, the influences of some controllable parameters on geometric phase are evaluated. The feasibility and challenge of distinguishing geometric effect in the POINT signal are also assessed in detail.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗