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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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

Mobility of singly-charged lanthanide cations in rare gases: Theoretical assessment of the state specificity

High quality, ab initio calculations are reported for the potential energy curves governing the interactions of four singly-charged lanthanide ions (Yb{sup +}, Eu{sup +}, Lu{sup +}, and Gd{sup +}) with the rare gases (RG = He–Xe). Scalar-relativistic coupled cluster calculations are used for the first three S-state ions, but for Gd{sup +}({sup 10}D°) it is necessary to take the interaction anisotropy into account with the help of the multi-reference technique. The potential energy curves are used to determine the ion mobility and other transport properties describing the motion of the ions through the dilute RG, both as functions of the temperature, T, in the low-field limit, and at fixed T as functions of the ratio of the electrostatic field strength to the gas number density, E/N. The calculated mobilities are in good agreement with the very limited experimental data that have become available recently. The calculations show a pronounced dependence of the transport properties on the electronic configuration of the ion, as well as a significant effect of the spin-orbit coupling on the transport properties of the Gd{sup +} ion, and predict that state-specific mobilities could be detectable in Gd{sup +}–RG experiments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2014

Calculation of State Specific Rate Coefficients for Non-Equilibrium Hypersonics Applications: from H(Psi) = E(Psi) to k(T) = A *exp(-E(sub a)/RT)

Development of High-Fidelity Physics-Based Models to describe hypersonic flight through the atmospheres of Earth and Mars is underway at NASA Ames Research Center. The goal is to construct chemistry models of the collisional and radiative processes that occur in the bow shock and boundary layers of spacecraft during atmospheric entry that are free of empiricism. In this talk I will discuss our philosophy and describe some of our progress. Topics to be covered include thermochemistry, internal energy relaxation, collisional dissociation and radiative emission and absorption. For this work we start by solving the Schrodinger equation to obtain accurate interaction potentials and radiative properties. Then we invoke classical mechanics to compute state-specific heavy particle collision cross sections and reaction rate coefficients. Finally, phenomenological rate coefficients and relaxation times are determined from master equation solutions.

aerothermodynamics↗
DOE OSTI2023

Time-resolving state-specific molecular dissociation with XUV broadband absorption spectroscopy

The electronic and nuclear dynamics inside molecules are essential for chemical reactions, where different pathways typically unfold on ultrafast timescales. Extreme ultraviolet (XUV) light pulses generated by free-electron lasers (FELs) allow atomic-site and electronic-state selectivity, triggering specific molecular dynamics while providing femtosecond resolution. Yet, time-resolved experiments are either blind to neutral fragments or limited by the spectral bandwidth of FEL pulses. Here, we combine a broadband XUV probe pulse from high-order harmonic generation with an FEL pump pulse to observe dissociation pathways leading to fragments in different quantum states. We temporally resolve the dissociation of a specific O 2 + state into two competing channels by measuring the resonances of ionic and neutral fragments. This scheme can be applied to investigate convoluted dynamics in larger molecules relevant to diverse science fields.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

N 5 -Scaling Excited-State-Specific Perturbation Theory

In this paper, we show that by working in a basis similar to that of the natural transition orbitals and using a modified zeroth-order Hamiltonian, the cost of a recently introduced perturbative correction to excited-state mean field theory can be reduced from seventh to fifth order in the system size. The (occupied) 2 (virtual) 3 asymptotic scaling matches that of ground-state second-order Møller-Plesset theory but with a significantly higher prefactor because the bottleneck is iterative: it appears in the Krylov-subspace-based solution of the linear equation that yields the first-order wave function. Here, we discuss the details of the modified zeroth-order Hamiltonian we use to reduce the cost and the automatic code generation process we used to derive and verify the cost scaling of the different terms. Overall, we find that our modifications have little impact on the method's accuracy, which remains competitive with singles and doubles equation-of-motion coupled cluster.

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

Exploring Ligand-to-Metal Charge-Transfer States in the Photo-Ferrioxalate System Using Excited-State Specific Optimization

The photo-ferrioxalate system (PFS), [Fe(III)(C 2 O 4 )] 3– , more than an exact chemical actinometer, has been extensively applied in wastewater and environment treatment. Despite many experimental efforts to improve clarity, important aspects of the mechanism of ferrioxalate photolysis are still under debate. In this paper, we employ the recently developed WΓ-CASSCF to investigate the ligand-to-metal charge-transfer states that are key to ferrioxalate photolysis. This investigation provides a qualitative picture of these states and key potential energy surface features related to the photolysis. Furthermore, our theoretical results are consistent with the prompt charge-transfer picture seen in recent experiments and clarify some features that are not visible in experiments. Two ligand-to-metal charge-transfer states contribute to the photolysis of ferrioxalate, and the avoided crossing barrier between them is low compared with the initial photoexcitation energy. Our data also clarify that one Fe–O bond cleaves first, followed by the C–C bond and the other Fe–O bond.

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

State-specific tunneling lifetimes from classical trajectories: H-atom dissociation in electronically excited pyrrole

A trajectory method of calculating tunneling probabilities from phase integrals along straight line tunneling paths, originally suggested by Makri and Miller [J. Chem. Phys. 91, 4026 (1989)] and recently implemented by Truhlar and co-workers [Chem. Sci. 5, 2091 (2014)], is tested for one- and two-dimensional ab initio based potentials describing hydrogen dissociation in the {sup 1}B{sub 1} excited electronic state of pyrrole. The primary observables are the tunneling rates in a progression of bending vibrational states lying below the dissociation barrier and their isotope dependences. Several initial ensembles of classical trajectories have been considered, corresponding to the quasiclassical and the quantum mechanical samplings of the initial conditions. It is found that the sampling based on the fixed energy Wigner density gives the best agreement with the quantum mechanical dissociation rates.

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

Overcoming resistance to HER2 inhibitors through state-specific kinase binding

The heterodimeric receptor tyrosine kinase complex formed by HER2 and HER3 can act as an oncogenic driver and is also responsible for rescuing a large number of cancers from a diverse set of targeted therapies. Inhibitors of these proteins, particularly HER2, have dramatically improved patient outcomes in the clinic, but recent studies have demonstrated that stimulating the heterodimeric complex, either via growth factors or by increasing the concentrations of HER2 and HER3 at the membrane, significantly diminishes the activity of the inhibitors. To identify an inhibitor of the active HER2–HER3 oncogenic complex, we developed a panel of Ba/F3 cell lines suitable for ultra-high-throughput screening. We report medicinal chemistry on the hit scaffold resulted in a previously uncharacterized inhibitor that acts through preferential inhibition of the active state of HER2 and, as a result, is able to overcome cellular mechanisms of resistance such as growth factors or mutations that stabilize the active form of HER2.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Accurate core excitation and ionization energies from a state-specific coupled-cluster singles and doubles approach

Here, we investigate the use of orbital-optimized references in conjunction with single-reference coupled-cluster theory with single and double substitutions (CCSD) for the study of core excitations and ionizations of 18 small organic molecules, without the use of response theory or equation-of-motion (EOM) formalisms. Three schemes are employed to successfully address the convergence difficulties associated with the coupled-cluster equations, and the spin contamination resulting from the use of a spin symmetry-broken reference, in the case of excitations. In order to gauge the inherent potential of the methods studied, an effort is made to provide reasonable basis set limit estimates for the transition energies. Overall, we find that the two best-performing schemes studied here for ΔCCSD are capable of predicting excitation and ionization energies with errors comparable to experimental accuracies. The proposed ΔCCSD schemes reduces statistical errors against experimental excitation energies by more than a factor of two when compared to the frozen-core core–valence separated (FC-CVS) EOM-CCSD approach – a successful variant of EOM-CCSD tailored towards core excitations.

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

A functional selectivity mechanism at the serotonin-2A GPCR involves ligand-dependent conformations of intracellular loop 2

With recent progress in determination of G protein-coupled receptor (GPCR) structure with crystallography, a variety of other experimental approaches (e.g., NMR spectroscopy, fluorescent-based assays, mass spectrometry techniques) are also being used to characterize state-specific and ligand-specific conformational states. MD simulations offer a powerful complementary approach to elucidate the dynamic features associated with ligand-specific GPCR conformations. To shed light on the conformational elements and dynamics of the important aspect of GPCR functional selectivity, we carried out unbiased microsecond-length MD simulations of the human serotonin 2A receptor (5-HT 2A R) in the absence of ligand and bound to four distinct serotonergic agonists. The 5-HT 2A R is a suitable system to study the structural features involved in the ligand-dependent conformational heterogeneity of GPCRs because it is well-characterized experimentally and exhibits a strong agonist-specific phenotype in that some 5-HT 2A R agonists induce LSD-like hallucinations, while others lack this psychoactive property entirely. Here we report evidence for structural and dynamic differences in 5-HT 2A R interacting with such pharmacologically distinct ligands, hallucinogens, and nonhallucinogens obtained from all-atom MD simulations. Differential ligand binding contacts were identified for structurally similar hallucinogens and nonhallucinogens and found to correspond to different conformations in the intracellular loop 2 (ICL2). From the different ICL2 conformations, functional selective phenotypes are suggested through effects on dimerization and/or distinct direct interaction with effector proteins. Lastly, the findings are presented in the context of currently proposed hallucinogenesis mechanisms, and ICL2 is proposed as a fine-tuning selective switch that can differentiates modes of 5-HT 2A R activation.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Linearized Pair-Density Functional Theory for Vertical Excitation Energies

Multiconfiguration pair-density functional theory (MC-PDFT) is a computationally efficient method that computes the energies of electronic states in a state specific or state average framework via an on-top functional. However, MC-PDFT does not include state interaction among these states since the final energies do not come from the diagonalization of an effective model-space Hamiltonian. Recently, multistate extensions such as linearized PDFT (L-PDFT) have been developed to accurately model the potentials near conical intersections and avoided crossings. However, there has not been any systematic study evaluating their performance for predicting vertical excitations at the equilibrium geometry of a molecule, when the excited states are generally well separated. In this paper, we report the performance of L-PDFT on the extensive QUESTDB data set of vertical excitations using a database of automatically selected active spaces. We show that L-PDFT performs well on all these excitations and successfully reproduces the performance of MC-PDFT. These results further demonstrate the potential of L-PDFT, as its scaling is constant with the number of states included in the state-average manifold, whereas MC-PDFT scales linearly in this regard.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Towards an Analysis of the GhostFluid Method

The GhostFluid method is built on the premise that a material interface, such as that shown in Figure 1 (a), can be discretized as two distinct materials that communicate, indirectly, via ghostcells. The situation is shown pictorially in Figure 1 (b). The attraction of the approach is that the two halves of the problem can be integrated using a regular, single material scheme, with none of the complex, book-keeping normally associated with a multi-material solver. On the down side, the reliability of the approach rests with the filling of the ghost states. Specifically, the states must be chosen such that the resultant evolution is consistent with the full problem, and for non-linear systems, there is no guarantee that satisfactory states actually exist.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Globally Averaged Atmospheric CFC-11 Concentrations: Monthly and Annual Data for the Period 1975-1992 (DB1010)

This data set presents globally averaged atmospheric concentrations of chlorofluorocarbon 11, known also as CFC-11 or F-11 (chemical name: trichlorofluoromethane; formula: CCl3F). The monthly global average data are derived from flask air samples collected at eight sites in six locations over the period August 1980-July 1992. The sites are Barrow (Alaska), Cape Meares (Oregon), Cape Kumukahi and Mauna Loa (Hawaii), Cape Matatula (American Samoa), Cape Grim (Tasmania), Palmer Station, and the South Pole (Antarctica). At each collection site, monthly averages were obtained from three flask samples collected every week. In addition to the monthly global averages available for 1980-992, this data set also contains annual global average data for 1975-1985. These annual global averages were derived from January measurements at the South Pole and in the Pacific Northwest of the United States (specifically, Washington state and the Oregon coast).For access to the data files, click this link to the CDIAC data transition website: http://cdiac.ess-dive.lbl.gov/ndps/db1010.html

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2016

Development of a two-dimensional binning model for N{sub 2}–N relaxation in hypersonic shock conditions

A high fidelity internal energy relaxation model for N{sub 2}–N suitable for use in direct simulation Monte Carlo (DSMC) modeling of chemically reacting flows is proposed. A novel two-dimensional binning approach with variable bin energy resolutions in the rotational and vibrational modes is developed for treating the internal mode of N{sub 2}. Both bin-to-bin and state-specific relaxation cross sections are obtained using the molecular dynamics/quasi-classical trajectory (MD/QCT) method with two potential energy surfaces as well as the state-specific database of Jaffe et al. The MD/QCT simulations of inelastic energy exchange between N{sub 2} and N show that there is a strong forward-preferential scattering behavior at high collision velocities. The 99 bin model is used in homogeneous DSMC relaxation simulations and is found to be able to recover the state-specific master equation results of Panesi et al. when the Jaffe state-specific cross sections are used. Rotational relaxation energy profiles and relaxation times obtained using the ReaxFF and Jaffe potential energy surfaces (PESs) are in general agreement but there are larger differences between the vibrational relaxation times. These differences become smaller as the translational temperature increases because the difference in the PES energy barrier becomes less important.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Nuclear Safeguards Reporting System Requirements Specification

States enter into safeguards agreements with the International Atomic Energy Agency (IAEA) to fulfill their nuclear non-proliferation commitments. Each nonnuclear-weapon State party to the Treaty on the Non-Proliferation of Nuclear Weapons (NPT) [1] is required, pursuant to Article III, to conclude a comprehensive safeguards agreement (CSA) with the IAEA. This document aims to provide information regarding the system requirements of software designed for comprehensive safeguards reporting.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗
DOE OSTI2019

Tracking Excited States in Wave Function Optimization Using Density Matrices and Variational Principles

We introduce an approach for finding individual excited states' energy stationary points in complete active space self-consistent field theory that is compatible with standard optimization methods and highly effective at overcoming difficulties due to root flipping and near-degeneracies. Inspired by both the maximum overlap method and recent progress in excited-state variational principles, our approach combines these ideas in order to track individual excited states throughout the orbital optimization process. In a series of tests involving root flipping, near-degeneracies, charge transfers, and double excitations, we show that this approach is more effective for state-specific optimization than either the naive selection of roots on the basis of energy ordering or a more direct generalization of the maximum overlap method. We offer evidence that this state-specific approach improves the performance of complete active space perturbation theory for vertical excitation energies. Furthermore, we find that the state-specific optimization can help avoid state-averaging-induced discontinuities on potential energy surfaces. With a simple implementation, a low cost, and compatibility with large active space methods, the approach is designed to be useful in a wide range of excited-state investigations.

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

Monte Carlo simulation of nitrogen dissociation based on state-resolved cross sections

State-resolved analyses of N + N{sub 2} are performed using the direct simulation Monte Carlo (DSMC) method. In describing the elastic collisions by a state-resolved method, a state-specific total cross section is proposed. The state-resolved method is constructed from the state-specific total cross section and the rovibrational state-to-state transition cross sections for bound-bound and bound-free transitions taken from a NASA database. This approach makes it possible to analyze the rotational-to-translational, vibrational-to-translational, and rotational-to-vibrational energy transfers and the chemical reactions without relying on macroscopic properties and phenomenological models. In nonequilibrium heat bath calculations, the results of present state-resolved DSMC calculations are validated with those of the master equation calculations and the existing shock-tube experimental data for bound-bound and bound-free transitions. In various equilibrium and nonequilibrium heat bath conditions and 2D cylindrical flows, the DSMC calculations by the state-resolved method are compared with those obtained with previous phenomenological DSMC models. In these previous DSMC models, the variable soft sphere, phenomenological Larsen-Borgnakke, quantum kinetic, and total collision energy models are considered. From these studies, it is concluded that the state-resolved method can accurately describe the rotational-to-translational, vibrational-to-translational, and rotational-to-vibrational transfers and quasi-steady state of rotational and vibrational energies in nonequilibrium chemical reactions by state-to-state kinetics.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗