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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 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Association Kinetics for Perfluorinated n -Alkyl Radicals

Radical-radical reaction channels are important in the pyrolysis and oxidation chemistry of perfluoroalkyl substances (PFAS). In particular, unimolecular dissociation reactions within unbranched n-perfluoroalkyl chains, and their corresponding reverse barrierless association reactions, are expected to be significant contributors to the gas-phase thermal decomposition of families of species such as perfluorinated carboxylic acids and perfluorinated sulfonic acids. Unfortunately, experimental data for these reactions are scarce and uncertain. Furthermore, obtaining reliable theoretical predictions for such reactions is a laborious and computationally intensive task. Here, in this work, the chemical kinetics of the various association/decomposition reactions producing/decomposing the C 2 -C 4 series of unbranched n-perfluoroalkanes (C 2 F 6 , C 3 F 8 , and C 4 F 10 ) are examined using state-of-the-art ab initio transition-state-theory-based master-equation calculations. The variable-reaction-coordinate transition-state theory (VRC-TST) formalism is employed in computing the microcanonical and canonical rates for the association reactions. Reaction thermochemistry is obtained via composite quantum chemistry calculations and the laddering of error-canceling reaction schemes via a connectivity-based hierarchy approach employing ANL1/ANL0-style reference energies. Lennard-Jones collision model parameters for the considered systems were estimated by a direct dynamics approach, and collisional energy transfer parameters were obtained from analogies to systems of similar size and heavy-atom connectivity. A one-dimensional master equation approach was used to convert the microcanonical rate coefficients from the VRC-TST analysis into temperature- and pressure-dependent rate constants for the association reactions and the reverse dissociation reactions. The data are reported in standardized formats for usage in comprehensive chemical kinetic models for PFAS thermal destruction.

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

The neutron number probability distribution in coupled lumped assemblies

Here, the validity of the gamma distribution in describing the neutron number probability distribution function for both isolated and coupled multiplying assemblies when constrained to reproduce the true mean and variance is investigated in lumped geometry by numerical comparison with kinetic Monte Carlo simulations. The mean and variance are obtained from numerical solution of moment equations constructed from the relevant forward Master equation with assembly coupling coefficients obtained from a view factor method. Numerical results for a two-group, two coupled assemblies model, with static and dynamic reactivity insertion, show that except for subcritical assemblies, the gamma distribution well-approximates the number distribution. Differences in the fast and thermal neutron population shapes are explained in terms of effective source strengths due to downscatter and coupling.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2024

Implementation of new mixture rules has a substantial impact on combustion predictions for H 2 and NH 3

Complex-forming reactions comprise a substantial fraction of all important combustion reactions and are central to combustion behavior. Despite being often called “pressure-dependent” reactions, their rate constants depend on not only the pressure but also the composition. While modern combustion codes allow arbitrarily high accuracy in treating pressure dependence, recent work has consistently demonstrated dramatic failures of essentially all available treatments of mixture dependence. In situations where mixture dependence is treated at all, it is inevitably treated through specification of pressure-dependent rate constants for a set of pure bath gases, which are then combined to estimate the rate constant in a mixture via a “mixture rule.” While there had been a generally unquestioning confidence in these mixture rules, they had, in reality, been scarcely tested until the last decade, when comparisons against master equation calculations revealed order-of-magnitude errors for important pressure-dependent reactions. New mixture rules, based on the reduced pressure, have recently been proposed and shown to reproduce master equation calculations for broad classes of complex-forming reactions very accurately. Here, in this work, we present an implementation of one such new mixture rule (“LMR-R”) in Cantera and then use it to enable simulations that use new high-accuracy ab initio data for individual bath gases (for the first time, since codes previously could not accommodate the complex bath gas dependence). Demonstrations focus on combustion of H 2 and NH 3 , where (1) high-accuracy ab initio data are available and (2) the impact is expected to be large due to the high fractions of efficient colliders (e.g., H 2 O and NH 3 ) in the burned and unburned gases. Indeed, we find the impact of this treatment to be substantial and may explain previous modeling difficulties for these important carbon-free fuels, particularly for NH 3 , whose extraordinarily high third-body efficiency (~20) is often omitted from kinetic models.

Ammonia↗
DOE OSTI2022

A simple improved low temperature correction for the hierarchical equations of motion

The study of open system quantum dynamics has been transformed by the hierarchical equations of motion (HEOM) method, which gives the exact dynamics for a system coupled to a harmonic bath at arbitrary temperature and system–bath coupling strength. However, in its standard form, this method is only consistent with the weak-coupling quantum master equation at all temperatures when many auxiliary density operators are included in the hierarchy, even when low temperature corrections are included. Here, we propose a new low temperature correction scheme for the termination of the hierarchy based on Zwanzig projection, which alleviates this problem and restores consistency with the weak-coupling master equation with a minimal hierarchy. The utility of the new correction scheme is demonstrated on a range of model systems, including the Fenna–Matthews–Olson complex. The new closure is found to improve convergence of the HEOM even beyond the weak-coupling limit and is very straightforward to implement in existing HEOM codes.

Fay, Thomas P. (ORCID:000000030625731X)↗
DOE OSTI2026

Kinetic Model of HoxEFU reduction by NADH [SWR-26-087]

This repository is used to release code generated for manuscripts on the Photosynthetic Energy Transduction core program. This code simulates the reduction of HoxEFU by NADH. The electro transfer rate constants for the simulation are specified in the .csv files. The two .csv files correspond tot he two models described in Dawson et al. Cell. Rep. Phys. Sci. 2026. The code utilizes a chemical master equation, a set of differential equations, defining the time evolution of the oxidation and reduction kinetics of NAD+, NADH, a FMN flavin, and a set of iron sulfur clusters. The kinetics of HoxEFU reduction by NADH are evaluated by numerical integration of the chemical master equation using a variable-time-step Runge-Kutta algorithm.

Dahl, Peter [National Laboratory of the Rockies (N↗
DOE OSTI2020

On the advantages of exploiting memory in Markov state models for biomolecular dynamics

Biomolecular dynamics play an important role in numerous biological processes. Markov State Models (MSMs) provide a powerful approach to study these dynamic processes by predicting long time scale dynamics based on many short molecular dynamics (MD) simulations. In an MSM, protein dynamics are modeled as a kinetic process consisting of a series of Markovian transitions between different conformational states at discrete time intervals (called “lag time”). To achieve this, a master equation must be constructed with a sufficiently long lag time to allow interstate transitions to become truly Markovian. This imposes a major challenge for MSM studies of proteins since the lag time is bound by the length of relatively short MD simulations available to estimate the frequency of transitions. Here, we show how one can employ the generalized master equation formalism to obtain an exact description of protein conformational dynamics both at short and long time scales without the time resolution restrictions imposed by the MSM lag time. Using a simple kinetic model, alanine dipeptide, and WW domain, we demonstrate that it is possible to construct these quasi-Markov State Models (qMSMs) using MD simulations that are 5–10 times shorter than those required by MSMs. These qMSMs only contain a handful of metastable states and, thus, can greatly facilitate the interpretation of mechanisms associated with protein dynamics. A qMSM opens the door to the study of conformational changes of complex biomolecules where a Markovian model with a few states is often difficult to construct due to the limited length of available MD simulations.

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

Real-time dynamics of the Schwinger model as an open quantum system with Neural Density Operators

Ab-initio simulations of multiple heavy quarks propagating in a Quark-Gluon Plasma are computationally difficult to perform due to the large dimension of the space of density matrices. This work develops machine learning algorithms to overcome this difficulty by approximating exact quantum states with neural network parametrisations, specifically Neural Density Operators. As a proof of principle demonstration in a QCD-like theory, the approach is applied to solve the Lindblad master equation in the 1 + 1d lattice Schwinger Model as an open quantum system. Neural Density Operators enable the study of in-medium dynamics on large lattice volumes, where multiple-string interactions and their effects on string-breaking and recombination phenomena can be studied. Thermal properties of the system at equilibrium can also be probed with these methods by variationally constructing the steady state of the Lindblad master equation. Scaling of this approach with system size is studied, and numerical demonstrations on up to 32 spatial lattice sites and with up to 3 interacting strings are performed.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2020

Bayesian inference of Stochastic reaction networks using Multifidelity Sequential Tempered Markov Chain Monte Carlo

Stochastic reaction network models are often used to explain and predict the dynamics of gene regulation in single cells.These models usually involve several parameters, such as the kinetic rates of chemical reactions, that are not directly measurable and must be inferred from experimental data. Bayesian inference provides a rigorous probabilistic frame-work for identifying these parameters by finding a posterior parameter distribution that captures their uncertainty.Traditional computational methods for solving inference problems such as Markov Chain Monte Carlo methods based on classical Metropolis-Hastings algorithm involve numerous serial evaluations of the likelihood function, which in turn requires expensive forward solutions of the chemical master equation (CME). We propose an alternate approach based on a multifidelity extension of the Sequential Tempered Markov Chain Monte Carlo (ST-MCMC) sampler. This algorithm is built upon Sequential Monte Carlo and solves the Bayesian inference problem by decomposing it into a sequence of efficiently solved subproblems that gradually increase both model fidelity and the influence of the observed data. We reformulate the finite state projection (FSP) algorithm, a well-known method for solving the CME, to produce a hierarchy of surrogate master equations to be used in this multifidelity scheme. To determine the appropriate fidelity, we introduce a novel information-theoretic criteria that seeks to extract the most information about the ultimate Bayesian posterior from each model in the hierarchy without inducing significant bias. This novel sampling scheme is tested with high performance computing resources using biologically relevant problems.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2022

Stereoisomer-dependent unimolecular kinetics of 2,4-dimethyloxetanyl peroxy radicals

2,4,dimethyloxetane is an important cyclic ether intermediate that is produced from hydroperoxyalkyl (QOOH) radicals in the low-temperature combustion of n-pentane. However, the reaction mechanisms and rates of consumption pathways remain unclear. In the present work, the pressure- and temperature-dependent kinetics of seven cyclic ether peroxy radicals, which stem from 2,4,dimethyloxetane via H-abstraction and O 2 addition, were determined. The automated kinetic workflow code, KinBot, was used to model the complexity of the chemistry in a stereochemically resolved manner and solve the resulting master equations from 300–1000 K and from 0.01–100 atm. The main conclusions from the calculations include (i) diastereomeric cyclic ether peroxy radicals show significantly different reactivities, (ii) the stereochemistry of the peroxy radical determines which QOOH isomerization steps are possible, (iii) conventional QOOH decomposition pathways, such as cyclic ether formation and HO 2 elimination, compete with ring-opening reactions, which primarily produce OH radicals, the outcome of which is sensitive to stereochemistry. Ring-opening reactions lead to unique products, such as unsaturated, acyclic peroxy radicals, that form direct connections with species present in other chemical kinetics mechanisms through "cross-over" reactions that may complicate the interpretation of experimental results from combustion of n-pentane and, by extension, other alkanes. For example, one cross-over reaction involving 1-hydroperoxy-4-pentanone-2-yl produces 2-(hydroperoxymethyl)-3-butanone-1-yl, which is an iso-pentane-derived ketohydroperoxide (KHP). At atmospheric pressure, the rate of chemical reactions of all seven peroxy radicals compete with that of collisional stabilization, resulting in well-skipping reactions. However, at 100 atm, only one out of seven peroxy radicals undergoes significant well-skipping reactions. Here, the rates produced from the master equation calculations provide the first foundation for the development of detailed sub-mechanisms for cyclic ether intermediates. In addition, analysis of the complex reaction mechanisms of 2,4-dimethyloxetane-derived peroxy radicals provides insights into the effects of stereoisomers on reaction pathways and product yields.

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

Identifiability and characterization of transmon qutrits through Bayesian experimental design

Robust control of a quantum system is essential to utilize the current noisy quantum hardware to its full potential, such as quantum algorithms. To achieve such a goal, a systematic search for an optimal control for any given experiment is essential. The design of optimal control pulses requires accurate numerical models and, therefore, accurate characterization of the system parameters. We present an online Bayesian approach for quantum characterization of qutrit systems, which automatically and systematically identifies optimal experiments that provide maximum information on the system parameters, thereby greatly reducing the number of experiments that need to be performed on the quantum testbed. Unlike most characterization protocols that provide point-estimates of the parameters, the proposed approach is able to estimate their probability distribution. The applicability of the Bayesian experimental design technique was demonstrated on test problems, where each experiment was defined by a parameterized control pulse. In addition to this, we also present an approach for iterative pulse extension, which is robust under uncertainties in transition frequencies and coherence times, and shot noise, despite being initialized with wide uninformative priors. Furthermore, we provide a mathematical proof of the theoretical identifiability of the model parameters and present conditions on the quantum state under which the parameters are identifiable. The proof and conditions for identifiability are presented for both closed and open quantum systems using the Schrödinger equation and the Lindblad master equation, respectively.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2026

JIMWLK on a quantum computer

We propose a method for solving the Jalilian-Marian-Iancu-McLerran-Weigert-Leonidov-Kovner (JIMWLK) evolution equation on quantum computers. Our approach exploits the reformulation of the JIMWLK equation as a Lindblad master equation governing the rapidity evolution of the hadronic density matrix, as established in prior work. To render the problem tractable for quantum simulation, we introduce several approximations: the two-dimensional transverse plane is reduced to a one-dimensional radial lattice by assuming azimuthal symmetry of the jump operators; the gauge group is restricted to SU(2); and the infinite Wilson lines of the JIMWLK equation are replaced by finite Wilson links along the light-cone direction. The resulting bosonic Hilbert space is truncated using the electric field basis familiar from Hamiltonian lattice gauge theory, with states restricted to angular momenta 𝑗 ≤ 𝑗 max . We derive the matrix elements of the JIMWLK Lindblad jump operators in this basis. As a benchmark, we demonstrate rapid convergence of the fundamental dipole expectation value with 𝑗 max for both pure and mixed Gaussian initial density matrices. For the simplest truncation, 𝑗 max =1/2, we implement the Lindblad evolution using a quantum simulation algorithm verified with the Qiskit statevector simulator by decomposing the non-unitary evolution operator into a linear combination of unitaries. This work establishes a concrete pathway toward quantum simulation of high-energy quantum chromodynamics evolution equations, with direct relevance to the physics program of the Electron-Ion Collider.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2020

Eikonal black hole ringings in generalized energy-momentum squared gravity

In the scope of black hole spectroscopy, several attempts have been made in the past decades to test black holes or gravitational theories via black hole quasinormal modes. In the eikonal approximation, the quasinormal modes are generically associated with the photon ring of the black hole. This correspondence is valid for most cases in general relativity, but may not be true in other theories of gravity. In this paper, we consider the generalized energy-momentum squared gravity in which matter fields are nonminimally coupled to geometry. We investigate the axial perturbations of the charged black holes in this model, without assuming any explicit expression of the action functional. After obtaining the modified Klein-Gordon equation and the modified Maxwell equations, we perturb the gravitational equations and the modified Maxwell equations to derive the coupled master equations of the axial perturbations. In the presence of the nonminimal coupling between matter and geometry, the correspondence between the eikonal quasinormal modes and the photon ring is not satisfied in general. Also, the two coupled fields of the axial perturbations are found to propagate independently, and they do not share the same quasinormal frequencies in the eikonal limit.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2024

Competing Radical and Molecular Channels in the Unimolecular Dissociation of Methylformate

The thermal dissociation of methylformate has been characterized by numerous experimental and theoretical studies that all seem to agree that the lowest energetically accessible process is a 3-center H-atom transfer that leads to the molecular products CH3OH 3 OH + CO. However, these literature studies seem to be at odds with regards to the role of other competing molecular eliminations and bond-fission processes and therefore a complete and resolved mechanistic picture of methylformate thermal dissociation still eludes us. In this work, we have performed high-level electronic structure theory calculations to characterize the energetics of other overlooked molecular and radical processes that can originate on the complex CH3OCHO 3 OCHO potential energy surface (PES). The present calculations do indeed confirm that the lowest energy process accessible on this PES is molecular elimination to form CH3OH 3 OH + CO. However, unlike prior theoretical studies, the present calculations reveal that the second lowest energy process is a 5-center concerted elimination process that leads to the direct formation of H2 2 + CH2O 2 O + CO. We also note that HCO2 2 from the lowest-lying bond fission has two energetically comparable electronic states (of 2 B 2 and 2 A 1 symmetry). Furthermore, the barrier for H-atom migration of CH3OCHO 3 OCHO to form the carbene (CH3OCOH) 3 OCOH) is similar to that for the direct 4-center elimination process leading to CH2O 2 O + CH2O 2 O characterized in prior literature studies. Radical and molecular pathways to CH3 3 + HOCO and CH4 4 + CO2 2 can also be facilitated from this carbene. Master equation calculations were performed to characterize the competition between the various molecular and radical processes on this more elaborate CH3OCHO 3 OCHO PES. The results of the present theoretical analyses were used to resolve outstanding questions on the role of secondary radical- initiated reactions in characterizing prior literature experimental studies.

Chemical Kinetics↗
DOE OSTI2021

Quantum system dynamics with a weakly nonlinear Josephson junction bath

Here, we investigate the influence of a weakly nonlinear Josephson bath consisting of a chain of Josephson junctions on the dynamics of a small quantum system (LC oscillator). Focusing on the regime where the charging energy is the largest energy scale, we perturbatively calculate the correlation function of the Josephson bath to the leading order in the Josephson energy divided by the charging energy while keeping the cosine potential exactly. When the variation of the charging energy along the chain ensures fast decay of the bath correlation function, the dynamics of the LC oscillator that is weakly and capacitively coupled to the Josephson bath can be solved through the Markovian master equation. We establish a duality relation for the Josephson bath between the regimes of large charging and Josephson energies, respectively. The results can be applied to cases where the charging energy either is nonuniformly engineered or disordered in the chain. Furthermore, we find that the Josephson bath may become non-Markovian when the temperature is increased beyond the zero-temperature limit in that the bath correlation function gets shifted by a constant and does not decay with time.

1-dimensional systems↗
DOE OSTI2025

Current-based metrology with two-terminal mesoscopic conductors

The traditional approach to quantum parameter estimation focuses on the quantum state, deriving fundamental bounds on precision through the quantum Fisher information. In most experimental settings, however, performing arbitrary quantum measurements is highly unfeasible. In open quantum systems, an alternative approach to metrology involves the measurement of stochastic currents flowing from the system to its environment. However, the present understanding of current-based metrology is mostly limited to Markovian master equations. Considering a parameter estimation problem in a two-terminal mesoscopic conductor, we identify the key elements that determine estimation precision within the Landauer-Büttiker formalism. Crucially, this approach allows us to address arbitrary coupling and temperature regimes. Furthermore, we obtain analytical results for the precision in linear-response and zero-temperature regimes. For the specific parameter estimation task that we consider, we demonstrate that the boxcar transmission function is optimal for current-based metrology in all parameter regimes.

Landauer formula↗
DOE OSTI2020

Driven-dissipative quantum mechanics on a lattice: Simulating a fermionic reservoir on a quantum computer

The driven-dissipative many-body problem remains one of the most challenging unsolved problems in quantum mechanics. The advent of quantum computers may provide a unique platform for efficiently simulating such driven-dissipative systems. But, there are many choices for how one can engineer the reservoir. One can simply employ ancilla qubits to act as a reservoir and then digitally simulate them via algorithmic cooling. A more attractive approach, which allows one to simulate an infinite reservoir, is to integrate out the bath degrees of freedom and describe the driven-dissipative system via a master equation, that can also be simulated on a quantum computer. In this work, we consider the particular case of noninteracting electrons on a lattice driven by an electric field and coupled to a fermionic thermostat. Then, we provide two different quantum circuits: the first one reconstructs the full dynamics of the system using Trotter steps, while the second one dissipatively prepares the final nonequilibrium steady state in a single step. We run both circuits on the IBM quantum experience. For circuit (i), we achieved up to five Trotter steps. When partial resets become available on quantum computers, we expect that the maximum simulation time can be significantly increased. Lastly, the methods developed here suggest generalizations that can be applied to simulating interacting driven-dissipative systems.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Mechanism, thermochemistry, and kinetics of the reversible reactions: C 2 H 3 + H 2 ⇌ C 2 H 4 + H ⇌ C 2 H 5

High-level coupled cluster theory, in conjunction with Active Thermochemical Tables (ATcT) and E,J-resolved master equation calculations, was used in a study of the title reactions, which play an important role in the combustion of hydrocarbons. In the set of radical/radical reactions leading to soot formation in flames, the addition of H-atoms to alkenes is likely a common reaction, triggering the isomerization of complex hydrocarbons to aromatics. The heats of formation of C 2 H 3 , C 2 H 4 , and C 2 H 5 are established to be 301.26 ± 0.30 at 0 K (297.22 ± 0.30 at 298 K), 60.89 ± 0.11 (52.38 ± 0.11), and 131.38 ± 0.22 (120.63 ± 0.22) kJ mol -1 , respectively. The calculated rate constants from first principles agree well with experiments where they are available. Under conditions typical of high temperature combustion – where experimental work is very challenging with a consequent dearth of accurate data –here we provide high-level theoretical results for kinetic modeling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗