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Results for “Dynamical correlation”

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 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

A benchmark of Gutzwiller conjugate gradient minimization method in ground state energy calculations of dimers

Herein we present numerical results of ground-state energies of 9 molecules in the well-established G2 molecule set given by the Gutzwiller conjugate gradient minimization (GCGM) method. The method, beyond the commonly used Gutzwiller approximation, was recently developed based on Gutzwiller variational wave functions. We find that compared to benchmark data given by full configuration interaction, GCGM total energies are reasonably well reproduced with the minimum basis set. To include the dynamical correlation beyond the minimal basis calculations, we adopt the local density approximation for the dynamical correlation energy $E_c$. By comparing the results with benchmark data given by experiments and large-basis configuration interaction, the GCGM total energies with $E_c$ are in general better reproduced, but discrepancies are still observed for some dimers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Correlating Protein Dynamics and Catalytic Activity of a Model Hydrogenase Using Paramagnetic and Biological Nuclear Magnetic Resonance Spectroscopy

Rational catalyst design remains a significant challenge, with electronic structure, steric, and electrostatic effects known to contribute to activity. Recently, dynamics has been recognized as another factor that impacts catalysis, though identifying and predicting these effects has remained out of reach. Nickel-substituted rubredoxin (NiRd), a protein-based mimic of a hydrogenase enzyme, serves as a model catalytic system in which dynamics can be systematically investigated with respect to activity. While over 30 secondary-sphere mutants of NiRd have been shown to be catalytically active, no significant correlation was observed between the rates and catalytic overpotential or electronic structure, prompting questions about the protein-derived factors that modulate activity. Here, in this work, NMR spectroscopy was used to investigate the roles of substrate accessibility, protein dynamics, and protein stability in controlling catalysis. Significant paramagnetic effects from the nickel center (S = 1) isolate the methylene proton resonances of the metal-coordinating cysteine residues. The sensitivity of resonance positions and linewidths to local environment offers an opportunity to study dynamical molecular changes around the metal center with high resolution. Machine learning algorithms were employed to identify correlations between the catalytic activity and the paramagnetic NMR spectra. These analyses revealed spectroscopic features of specific cysteine protons that report on catalytic overpotential and increased turnover rates, which are further supported by the results obtained using high-field NMR techniques. Collectively, these studies indicate the potential for multifrequency NMR techniques to resolve key contributors to catalytic activity and highlight the importance of local and outer-sphere dynamics.

Protein Engineering↗
DOE OSTI2019

Distinguishing artificial and essential symmetry breaking in a single determinant: approach and application to the C 60 , C 36 , and C 20 fullerenes

We present a thorough analysis of symmetry breaking observed in Hartree–Fock (HF) solutions of the C 60 , C 36 , and C 20 fullerenes in order to characterize the nature of electron correlation in them. Our analysis is based on (1) the critical regularization strength to restore symmetry breaking in the recently developed regularized orbital optimized second-order Møller–Plesset perturbation theory (κ-OOMP2), (2) singlet–triplet gaps from various MP2 methods, and (3) natural orbital occupation numbers from restricted coupled-cluster with singles and doubles (RCCSD) and coupled-cluster valence bond with singles and doubles (CCVB-SD). Based on these three independent probes, we conclude that C 36 (D6h) exhibits genuine strong correlation and symmetry breaking whereas C 60 exhibits artificial HF symmetry breaking and is not strongly correlated. Investigating the critical regularization strength, we discuss strong correlation in C 20 at the Jahn–Teller distorted geometries (C 2h , D 2h , C i , and D 3h ) and the Ih geometry. Only C 20 (I h ) was found to be strongly correlated while others exhibit artificial HF symmetry breaking. This analysis highlights a useful feature of the recommended κ-OOMP2 method. It is an electronic structure method that describes dynamic correlation, and attenuates strong correlation in MP2 towards zero by regularization. Therefore, κ-OOMP2 will exhibit symmetry breaking in its reference determinant only when correlation is strong (i.e., essential symmetry breaking). Furthermore, artificial symmetry breaking (arising in HF due to neglect of dynamic correlation) thus appears to be removed in κ-OOMP2.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1991

Phi-s correlation and dynamic time warping - Two methods for tracking ice floes in SAR images

The authors present two algorithms for performing shape matching on ice floe boundaries in SAR (synthetic aperture radar) images. These algorithms quickly produce a set of ice motion and rotation vectors that can be used to guide a pixel value correlator. The algorithms match a shape descriptor known as the Phi-s curve. The first algorithm uses normalized correlation to match the Phi-s curves, while the second uses dynamic programming to compute an elastic match that better accommodates ice floe deformation. Some empirical data on the performance of the algorithms on Seasat SAR images are presented.

Mcconnell, Ross↗
DOE OSTI2020

Impact of dynamical chiral symmetry breaking and dynamical diquark correlations on proton generalized parton distributions

We calculate the leading-twist, helicity-independent generalized parton distributions (GPDs) of the proton, at finite skewness, in the Nambu–Jona-Lasinio (NJL) model of quantum chomodynamics (QCD). The NJL model reproduces low-energy characteristics of QCD, including dynamical chiral symmetry breaking (DCSB). The proton bound-state amplitude is solved for using the Faddeev equation in a quark-diquark approximation, including both dynamical scalar and axial vector diquarks. GPDs are calculated using a dressed non-local correlator, consistent with DCSB, which is obtained by solving a Bethe-Salpeter equation. The model and approximations used observe Lorentz covariance, and as a consequence the GPDs obey polynomiality sum rules. Extractions of electromagnetic and gravitational form factors are performed. We find a D-term of -1.08 when the non-local correlator is properly dressed, and 0.85 when the bare correlator is used instead, suggesting that within this framework proton stability requires the constituent quarks to be dressed consistently with DCSB. In conclusion, we also find that the anomalous gravitomagnetic moment vanishes, as required by Poincare symmetry.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
NASA NTRS1992

Development of Test-Analysis Models (TAM) for correlation of dynamic test and analysis results

The primary objective of structural analysis of aerospace applications is to obtain a verified finite element model (FEM). The verified FEM can be used for loads analysis, evaluate structural modifications, or design control systems. Verification of the FEM is generally obtained as the result of correlating test and FEM models. A test analysis model (TAM) is very useful in the correlation process. A TAM is essentially a FEM reduced to the size of the test model, which attempts to preserve the dynamic characteristics of the original FEM in the analysis range of interest. Numerous methods for generating TAMs have been developed in the literature. The major emphasis of this paper is a description of the procedures necessary for creation of the TAM and the correlation of the reduced models with the FEM or the test results. Herein, three methods are discussed, namely Guyan, Improved Reduced System (IRS), and Hybrid. Also included are the procedures for performing these analyses using MSC/NASTRAN. Finally, application of the TAM process is demonstrated with an experimental test configuration of a ten bay cantilevered truss structure.

Angelucci, Filippo↗
DOE OSTI2018

Properties of coupled-cluster equations originating in excitation sub-algebras

In this paper we discuss properties of single-reference coupled cluster (CC) equations associated with the existence of nilpotent sub-algebras of excitations that allow one to represent CC equations in a hybrid fashion where the cluster amplitudes associated with these sub-algebras can be obtained by solving corresponding eigenvalue problem. For closed-shell formulations analyzed in this paper, the hybrid representation of CC equations provides a natural way for extending concepts behind actives-spaces and seniority numbers to provide more accurate description of electron correlation effects. Moreover, new representation can be utilized to re-define iterative algorithms used to solve CC equations, especially for though cases defined by the presence of strong static and dynamic correlation effects. We will also explore invariance properties associated with the nilpotent sub-algebras to define a new class of CC approximations referred in this paper to as the nilpotent-flow-based CC methods. We illustrate the performance of these methods on the example of ground- and excited-state calculations for commonly used small benchmark systems.

Kowalski, Karol↗
DOE OSTI2019

Local correlated motions in aqueous solution of sodium chloride

Real-space motions of molecules and ions in an aqueous solution of sodium chloride are studied with high-resolution inelastic x-ray scattering. In this study, we focus on the correlated dynamics of water molecules and salt ions, instead of the instantaneous structure and the rotational and reorientation dynamics that have been studied using scattering techniques and optical spectroscopy, respectively. The real-space analysis in terms of the Van Hove function illustrates the effect of salt ions to slow down the local correlated dynamics of surrounding water in the hydration shells.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Revealing the nature of electron correlation in transition metal complexes with symmetry breaking and chemical intuition

Here, in this work, we provide a nuanced view of electron correlation in the context of transition metal complexes, reconciling computational characterization via spin and spatial symmetry breaking in single-reference methods with qualitative concepts from ligand-field and molecular orbital theories. These insights provide the tools to reliably diagnose the multi-reference character, and our analysis reveals that while strong (i.e., static) correlation can be found in linear molecules (e.g., diatomics) and weakly bound and antiferromagnetically coupled (monometal-noninnocent ligand or multi-metal) complexes, it is rarely found in the ground-states of mono-transition-metal complexes. This leads to a picture of static correlation that is no more complex for transition metals than it is, e.g., for organic biradicaloids. In contrast, the ability of organometallic species to form more complex interactions, involving both ligand-to-metal σ-donation and metal-to-ligand π-backdonation, places a larger burden on a theory's treatment of dynamic correlation. We hypothesize that chemical bonds in which inter-electron pair correlation is non-negligible cannot be adequately described by theories using MP2 correlation energies and indeed find large errors vs experiment for carbonyl-dissociation energies from double-hybrid density functionals. A theory's description of dynamic correlation (and to a less important extent, delocalization error), which affects relative spin-state energetics and thus spin symmetry breaking, is found to govern the efficacy of its use to diagnose static correlation.

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

Generation, dynamics, and correlations of the fission fragments' angular momenta

The generation of angular momentum in fissioning nuclei is not well understood. The predictions of different models disagree, particularly concerning the correlation between the fragments' angular momenta. In this article, a time-dependent collective Hamiltonian model is proposed to treat the generation of the angular momentum in the fission fragments due to the quantum uncertainty principle as well as the dynamics of the collective wave function during and after scission. The model is constructed in the framework of the frozen Hartree-Fock approximation using a Skyrme energy functional to extract deformations of the fission fragments as well as the interactions in a derived collective Hamiltonian. The fission reactions studied are $^{240}$Pu $\rightarrow$ $^{132}$Sn+$^{108}$Ru and $^{240}$Pu $\rightarrow$ $^{144}$Ba+$^{96}$Sr. The model can account for a large part of the angular momentum found in experimental data. The orientation of the angular momentum of each fragment is found to be mainly in the plane perpendicular to the fission axis, in agreement with the experiment. The magnitudes of the angular momenta in the two fragments are nearly uncorrelated, in agreement with the recent experimental data of Wilson et al., Nature (London) 590, 566 (2021). Some of the conclusions of the traditional collective vibration model are supported by the present model but some are not. Surprisingly, it is found that the angular momenta of the fragments are slightly correlated positively as in a wriggling mode. As a result, it is also found that the presence of an octupole deformation in a fragment can significantly increase the generated angular momentum.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
NASA NTRS1979

Dynamic cross correlation studies of wave particle interactions in ULF phenomena

Magnetic field observations made by satellites in the earth's magnetic field reveal a wide variety of ULF waves. These waves interact with the ambient particle populations in complex ways, causing modulation of the observed particle fluxes. This modulation is found to be a function of species, pitch angle, energy and time. The characteristics of this modulation provide information concerning the wave mode and interaction process. One important characteristic of wave-particle interactions is the phase of the particle flux modulation relative to the magnetic field variations. To display this phase as a function of time a dynamic cross spectrum program has been developed. The program produces contour maps in the frequency time plane of the cross correlation coefficient between any particle flux time series and the magnetic field vector. This program has been utilized in several studies of ULF wave-particle interactions at synchronous orbit.

Mcpherron, R. L.↗
DOE OSTI2019

Quantum simulations of excited states with active-space downfolded Hamiltonians

Many-body techniques based on the double unitary coupled cluster ansatz (DUCC) can be used to downfold electronic Hamiltonians into low-dimensional active spaces. It can be shown that the resulting dimensionality reduced Hamiltonians are amenable for quantum computing. Recent studies performed for several benchmark systems using quantum phase estimation (QPE) algorithms demonstrated that these formulations can recover a significant portion of ground-state dynamical correlation effects that stem from the electron excitations outside of the active space. These results have also been confirmed in studies of ground-state potential energy surfaces using quantum simulators. In this letter, we study the effectiveness of the DUCC formalism in describing excited states. We also emphasize the role of the QPE formalism and its stochastic nature in discovering/identifying excited states or excited-state processes in situations when the knowledge about the true configurational structure of a sought after excited state is limited or postulated (due to the specific physics driving excited-state processes of interest). In this context, we can view the QPE algorithm as an engine for verifying various hypotheses for excited-state processes and providing statistically meaningful results that correspond to the electronic state(s) with the largest overlap with a postulated configurational structure. We illustrate these ideas on examples of strongly cor- related molecular systems, characterized by small energy gaps and high density of quasi-degenerate states around the Fermi level.

quantum chemistry, quantum computing, computationa↗
DOE OSTI2017

Time-dependent N -electron valence perturbation theory with matrix product state reference wavefunctions for large active spaces and basis sets: Applications to the chromium dimer and all-trans polyenes

In earlier work [A. Y. Sokolov and G. K.-L. Chan, J. Chem. Phys. 144, 064102 (2016)], we introduced a time-dependent formulation of the second-order N -electron valence perturbation theory (t-NEVPT2) which (i) had a lower computational scaling than the usual internally contracted perturbation formulation and (ii) yielded the fully uncontracted NEVPT2 energy. We present a combination of t-NEVPT2 with a matrix product state (MPS) reference wavefunction (t-MPS-NEVPT2) that allows us to compute uncontracted dynamic correlation energies for large active spaces and basis sets, using the time-dependent density matrix renormalization group algorithm. In addition, we report a low-scaling MPS-based implementation of strongly contracted NEVPT2 (sc-MPS-NEVPT2) that avoids computation of the four-particle reduced density matrix. We use these new methods to compute the dissociation energy of the chromium dimer and to study the low-lying excited states in all-trans polyenes (C 4 H 6 to C 24 H 26 ), incorporating dynamic correlation for reference wavefunctions with up to 24 active electrons and orbitals

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Revealing short- and long-range Li-ion diffusion in Li 2 MnO 3 from finite-temperature dynamical mean field theory

Li 2 MnO 3 is a key component of Li-excess layered cathodes of the form (1 − x), LiMO 2 + x, Li 2 MnO 3 (M = Mn, Ni, Co, …), yet its role in setting Li-ion transport limitations remains under debate. Here, in this study, we combine DFT+U, finite-temperature DFT+DMFT with a continuous-time quantum Monte Carlo impurity solver, and nudged-elastic-band (NEB) calculations to study Li + migration in paramagnetic Li 2 MnO 3 in the presence of a single Li vacancy. Evaluating DMFT total energies along the DFT+U NEB geometries reveals that dynamical correlations strongly renormalize the lowest-barrier processes, reducing the activation energies to E a = 0.18 eV for the shortest-range hop and E a = 0.50 eV for the next-lowest (transport-controlling) step. The 0.18 eV barrier quantitatively reproduces the short-range activation energy from µ+SR, while the 0.50 eV barrier is consistent with the long-range transport scale extracted from ac-impedance measurements. This single-vacancy, paramagnetic DMFT description thus provides a unified interpretation of local and macroscopic probes without invoking clustered vacancy configurations or strong extrinsic disorder, consistent with nearly stoichiometric Li 2 MnO 3 powders. More broadly, our results highlight finite-temperature dynamical correlations as an essential ingredient for predicting ionic migration energetics in correlated oxide electrodes.

Lee, Alex Taekyung [University of Illinois, Chicag↗
DOE OSTI2016

Size consistent formulations of the perturb-then-diagonalize Møller-Plesset perturbation theory correction to non-orthogonal configuration interaction

In this paper we introduce two size consistent forms of the non-orthogonal configuration interaction with second-order Møller-Plesset perturbation theory method, NOCI-MP2. We show that the original NOCI-MP2 formulation [S. R. Yost, T. Kowalczyk, and T. VanVoorh, J. Chem. Phys. 193, 174104 (2013)], which is a perturb-then-diagonalize multi-reference method, is not size consistent. We also show that this causes significant errors in large systems like the linear acenes. By contrast, the size consistent versions of the method give satisfactory results for singlet and triplet excited states when compared to other multi-reference methods that include dynamic correlation. For NOCI-MP2 however, the number of required determinants to yield similar levels of accuracy is significantly smaller. These results show the promise of the NOCI-MP2 method, though work still needs to be done in creating a more consistent black-box approach to computing the determinants that comprise the many-electron NOCI basis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗