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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 703 records · Page 39
All sourcesNASA NTRSDOE OSTI
NASA NTRS2004

Infrared Spectroscopy of Matrix-Isolated Polycyclic Aromatic Compounds and Their Ions: Phenazine, a Dual Substituted Polycyclic Aromatic Nitrogen Heterocycle - 7

The matrix-isolation technique has been employed to measure the mid-infrared spectra of phenazine (C12H8N2), a dual substituted Polycyclic Aromatic Nitrogen Heterocycle (PANH), in the neutral, cationic and anionic forms. The experimentally measured band frequencies and intensities are tabulated and compared with their calculated values as well as those of the non-substituted parent molecule, anthracene. The theoretical band positions and intensities were calculated using both the 3-31 G as well as the larger 6-3lG* Basis Sets. A comparison of the results can be found in the tables. The spectroscopic properties of phenazine and its cation are similar to those observed in mono-substituted PANHs, with one exception. The presence of a second nitrogen atom results in an additional enhancement of the cation's total integrated intensity, for the 1500-1000 cm(sup -1) (6.7 to 10 micron) region, over that observed for a mono-substituted PANH cation. The significance of this enhancement and the astrobiological implications of these results are discussed.

Mattioda, A. L.↗
NASA NTRS2007

Application of the Hilbert-Huang Transform to the Search for Gravitational Waves

We present the application of a novel method of time-series analysis, the Hilbert-Huang Transform, to the search for gravitational waves. This algorithm is adaptive and does not impose a basis set on the data, and thus the time-frequency decomposition it provides is not limited by time-frequency uncertainty spreading. Because of its high time-frequency resolution it has important applications to both signal detection and instrumental characterization. Applications to the data analysis of the ground and space based gravitational wave detectors, LIGO and LISA, are described.

Camp, Jordan B.↗
NASA NTRS2007

Low-energy Scattering of Positronium by Atoms

The survey reports theoretical studies involving positronium (Ps) - atom scattering. Investigations carried out in last few decades have been briefly reviewed in this article. A brief description of close-coupling approximation (CCA), the first-Born approximation (FBA) and the Born-Oppenheimer approximation (BOA) for Ps-Atom systems are made. The CCA codes of Ray et a1 [1-6] are reinvestigated using very fine mesh-points to search for resonances. The article advocates the need for an extended basis set & a systematic study using CCAs.

Ray, Hasi↗
NASA NTRS2007

Theoretical Studies of Routes to Synthesis of Tetrahedral N4

A paper [Chem. Phys. Lett. 345, 295 (2001)] describes theoretical studies of excited electronic states of nitrogen molecules, with a view toward utilizing those states in synthesizing tetrahedral N4, or Td N4 a metastable substance under consideration as a high-energy-density rocket fuel. Several ab initio theoretical approaches were followed in these studies, including complete active space self-consistent field (CASSCF), state-averaged CASSCF (SA-CASSCF), singles configuration interaction (CIS), CIS with second-order and third-order correlation corrections [CIS(D) and CIS(3)], and linear response singles and doubles coupled-cluster (LRCCSD). Standard double zeta polarized and triple zeta double polarized one-particle basis sets were used. The CASSCF calculations overestimated the excitation energies, while SACASSCF calculations partly corrected these overestimates. The accuracy of the CIS calculations varied, depending on the particular state, while the CIS(D), CIS(3), and LRCCSD results were in generally good agreement. The energies of the lowest six excited singlet states of Td N4 as calculated by the LRCCSD were compared with the energies of possible excited states of N2 + N2 fragments, leading to the conclusion that the most likely route for synthesis of Td N4 would involve a combination of two bound quintet states of N2.

Lee, Timothy J.↗
NASA NTRS2011

Highly Accurate Quartic Force Fields, Vibrational Frequencies, and Spectroscopic Constants for Cyclic and Linear C3H3(+)

High levels of theory have been used to compute quartic force fields (QFFs) for the cyclic and linear forms of the C H + molecular cation, referred to as c-C H + and I-C H +. Specifically the 33 3333 singles and doubles coupled-cluster method that includes a perturbational estimate of connected triple excitations, CCSD(T), has been used in conjunction with extrapolation to the one-particle basis set limit and corrections for scalar relativity and core correlation have been included. The QFFs have been used to compute highly accurate fundamental vibrational frequencies and other spectroscopic constants using both vibrational 2nd-order perturbation theory and variational methods to solve the nuclear Schroedinger equation. Agreement between our best computed fundamental vibrational frequencies and recent infrared photodissociation experiments is reasonable for most bands, but there are a few exceptions. Possible sources for the discrepancies are discussed. We determine the energy difference between the cyclic and linear forms of C H +, 33 obtaining 27.9 kcal/mol at 0 K, which should be the most reliable available. It is expected that the fundamental vibrational frequencies and spectroscopic constants presented here for c-C H + 33 and I-C H + are the most reliable available for the free gas-phase species and it is hoped that 33 these will be useful in the assignment of future high-resolution laboratory experiments or astronomical observations.

Huang, Xinchuan↗
NASA NTRS2011

Initiating Molecular Growth in the Interstellar Medium via Dimeric Complexes of Observed Ions and Molecules

A feasible initiation step for particle growth in the interstellar medium (ISM) is simulated by means of ab quantum chemistry methods. The systems studied are dimer ions formed by pairing nitrogen containing small molecules known to exist in the ISM with ions of unsaturated hydrocarbons or vice versa. Complexation energies, structures of ensuing complexes and electronic excitation spectra of the encounter complexes are estimated using various quantum chemistry methods. Moller-Plesset perturbation theory (MP2, Z-averaged perturbation theory (ZAP2), coupled cluster singles and doubles with perturbative triples corrections (CCSD(T)), and density functional theory (DFT) methods (B3LYP) were employed along with the correlation consistent cc-pVTZ and aug-cc-pVTZ basis sets. Two types of complexes are predicted. One type of complex has electrostatic binding with moderate (7-20 kcal per mol) binding energies, that are nonetheless significantly stronger than typical van der Waals interactions between molecules of this size. The other type of complex develops strong covalent bonds between the fragments. Cyclic isomers of the nitrogen containing complexes are produced very easily by ion-molecule reactions. Some of these complexes show intense ultraviolet visible spectra for electronic transitions with large oscillator strengths at the B3LYP, omegaB97, and equations of motion coupled cluster (EOM-CCSD) levels. The open shell nitrogen containing carbonaceous complexes especially exhibit a large oscillator strength electronic transition in the visible region of the electromagnetic spectrum.

Bera, Partha P.↗
NASA NTRS2015

MATRIX-VBS Condensing Organic Aerosols in an Aerosol Microphysics Model

The condensation of organic aerosols is represented in a newly developed box-model scheme, where its effect on the growth and composition of particles are examined. We implemented the volatility-basis set (VBS) framework into the aerosol mixing state resolving microphysical scheme Multiconfiguration Aerosol TRacker of mIXing state (MATRIX). This new scheme is unique and advances the representation of organic aerosols in models in that, contrary to the traditional treatment of organic aerosols as non-volatile in most climate models and in the original version of MATRIX, this new scheme treats them as semi-volatile. Such treatment is important because low-volatility organics contribute significantly to the growth of particles. The new scheme includes several classes of semi-volatile organic compounds from the VBS framework that can partition among aerosol populations in MATRIX, thus representing the growth of particles via condensation of low volatility organic vapors. Results from test cases representing Mexico City and a Finish forrest condistions show good representation of the time evolutions of concentration for VBS species in the gas phase and in the condensed particulate phase. Emitted semi-volatile primary organic aerosols evaporate almost completely in the high volatile range, and they condense more efficiently in the low volatility range.

Aerosols↗
NASA NTRS2015

Induction of Oxidation in Living Cells by Time-Varying Electromagnetic Fields

We are studying how biological systems can harness quantum effects of time varying electromagnetic (EM) waves as the time-setting basis for universal biochemical organization via the redox cycle. The effects of extremely weak EM field on the biochemical redox cycle can be monitored through real-time detection of oxidation-induced light emissions of reporter molecules in living cells. It has been shown that EM fields can also induce changes in fluid transport rates through capillaries (approximately 300 microns inner diameter) by generating annular proton gradients. This effect may be relevant to understanding cardiovascular dis-function in spaceflight, beyond the ionosphere. Importantly, we show that these EM effects can be attenuated using an active EM field cancellation device. Central for NASA's Human Research Program is the fact that the absence of ambient EM field in spaceflight can also have a detrimental influence, namely via increased oxidative damage, on DNA replication, which controls heredity.

oxidation↗
NASA NTRS2015

Unsteady Solution of Non-Linear Differential Equations Using Walsh Function Series

Walsh functions form an orthonormal basis set consisting of square waves. The discontinuous nature of square waves make the system well suited for representing functions with discontinuities. The product of any two Walsh functions is another Walsh function - a feature that can radically change an algorithm for solving non-linear partial differential equations (PDEs). The solution algorithm of non-linear differential equations using Walsh function series is unique in that integrals and derivatives may be computed using simple matrix multiplication of series representations of functions. Solutions to PDEs are derived as functions of wave component amplitude. Three sample problems are presented to illustrate the Walsh function series approach to solving unsteady PDEs. These include an advection equation, a Burgers equation, and a Riemann problem. The sample problems demonstrate the use of the Walsh function solution algorithms, exploiting Fast Walsh Transforms in multi-dimensions (O(Nlog(N))). Details of a Fast Walsh Reciprocal, defined here for the first time, enable inversion of aWalsh Symmetric Matrix in O(Nlog(N)) operations. Walsh functions have been derived using a fractal recursion algorithm and these fractal patterns are observed in the progression of pairs of wave number amplitudes in the solutions. These patterns are most easily observed in a remapping defined as a fractal fingerprint (FFP). A prolongation of existing solutions to the next highest order exploits these patterns. The algorithms presented here are considered a work in progress that provide new alternatives and new insights into the solution of non-linear PDEs.

Gnoffo, Peter A.↗
NASA NTRS2017

Feature Detection and Curve Fitting Using Fast Walsh Transforms for Shock Tracking: Applications

Walsh functions form an orthonormal basis set consisting of square waves. Square waves make the system well suited for detecting and representing functions with discontinuities. Given a uniform distribution of 2p cells on a one-dimensional element, it has been proven that the inner product of the Walsh Root function for group p with every polynomial of degree < or = (p - 1) across the element is identically zero. It has also been proven that the magnitude and location of a discontinuous jump, as represented by a Heaviside function, are explicitly identified by its Fast Walsh Transform (FWT) coefficients. These two proofs enable an algorithm that quickly provides a Weighted Least Squares fit to distributions across the element that include a discontinuity. The detection of a discontinuity enables analytic relations to locally describe its evolution and provide increased accuracy. Time accurate examples are provided for advection, Burgers equation, and Riemann problems (diaphragm burst) in closed tubes and de Laval nozzles. New algorithms to detect up to two C0 and/or C1 discontinuities within a single element are developed for application to the Riemann problem, in which a contact discontinuity and shock wave form after the diaphragm bursts.

Gnoffo, Peter A.↗
NASA NTRS2015

Energy and Spectroscopic Characterization of the Isomers of C4H3-, C6H3-, and C6H5-

Organic and inorganic molecules, neutral and ions have been observed in the interstellar medium. A few anions of organic molecules have also been observed recently. The Cassini spacecraft in the upper atmosphere of Titan has observed anions of large organic molecules. In this project we have studied the physical and spectroscopic properties of C4H3-, C6H3-, and C6H5-. We have optimized the geometrical structures of all low-lying isomers of the anions, calculated rotational, and harmonic vibrational frequencies of the anions mentioned above using the B3LYP density functional along with the augmented correlation consistent polar valence triple zeta (aug-cc-pVTZ) basis set. We have found many low-lying isomers on the potential energy surface of these anions.

Energy↗
NASA NTRS2016

The Low-Lying Electronic States of MgO

The low-lying singlet and triplet states of MgO have been studied using a SA-CASCF/ICMRCI approach using the aug-cc-pV5Z basis set. The spectroscopic constants (r(sub e), W(sub e), and T(sub e)) are in good agreement with the available experimental data. The computed lifetime for the B state is in excellent agreement with two of the three experimental results. The d state lifetime is in good agreement with experiment, while the computed D state lifetime is about twice as long as experiment.

Charles W Bauschlicher↗
NASA NTRS2018

Can Semi-Volatile Organic Aerosols Lead to Fewer Cloud Particles?

The impact of condensing organic aerosols on activated cloud number concentration is examined in a new aerosol microphysics box model, MATRIX-VBS. The model includes the volatility-basis set (VBS) framework coupled with the aerosol microphysical scheme MATRIX (Multiconfiguration Aerosol TRacker of mIXing state) that resolves aerosol mass and number concentrations and aerosol mixing state. By including the condensation of organic aerosols, the new model produces less activated particles compared to the original model, which treats organic aerosols as non-volatile. Parameters such as aerosol chemical composition, mass and number concentrations, and particle sizes which affect activated cloud number concentration are thoroughly tested via a suite of Monte-Carlo simulations. Results show that by considering semi-volatile organics in MATRIX-VBS, there is lower activated particle number concentration, except in cases with low cloud updrafts, in clean environment at above freezing temperatures, and in polluted environments at high temperature (310K) and extremely low humidity conditions.

Gao, Chloe Y.↗
NASA NTRS2021

Machine Learning the COSMO Model for Predicting Thermodynamics of Electrolyte Mixtures

Bottom-up design of electrolyte mixtures for battery systems requires predicting macro thermodynamic properties from molecular constituents. For instance, molten salt electrolyte batteries require conditions far above room temperature to operate. Therefore, discovering mixtures with increasingly lower eutectic melting points is desirable. A model that can approximate chemical activity is a valuable tool to search through the vast compositional design space. Machine learning can predict properties of materials such as vibrational free energies, electronic energy gaps, and thermal conductivities. Moreover, they can learn physical models such as interatomic potentials. The COSMO-SAC model uses theory and empirical parameterization to predict liquid-vapor and liquid-solid properties using first-principles calculations. However, obtaining activity coefficients required for parameterizing the COSMO-SAC model is costly and limited to a select chemical space. In this work, we explored if machine learning methods could improve the COSMO-SAC model and bridge density functional theory calculations to liquid phase thermodynamic properties. Our data-driven approach uses existing databases for sigma-profiles of organic solvents and reconciles their methodological differences via ensemble averaging. First, an optimal machine learning model is constructed for each dataset. Our machine learning algorithms use the sigma-profile as an input feature to predict binary mixtures' activity coefficients using multi-output regression. Each dataset uses different choices of functionals, methods, and basis sets. Therefore, our ensemble model attempts to predict corrected activity coefficients given the combination of all the model outputs. The activity coefficients used for training are generated using the COSMO-SAC model. This approach enables the extraction of meaningful information from the existing datasets to improve the COSMO-SAC model for obtaining thermodynamic properties of electrolyte mixtures. With the liquid phase activities, we can identify electrolyte mixtures that meet desired phase equilibria conditions.

Thermodynamics↗
NASA NTRS2019

Highly Accurate Quartic Force Field and Rovibrational Spectroscopic Constants for the Azirinyl Cation (c-C2NH2+) and Its Isomers

Azirinyl cation is an aromatic cyclic molecule that is isoelectronic with cyclopropenylidene, c-C3H2, and c-C3H3+. Cyclopropenylidene has been shown to be ubiquitous, existing in many different astrophysical environments. Given the similar chemistry between C and N, and the relative abundances between C and N in astrophysical environments, it is expected that there should be aromatic ringed molecules that incorporate N in the ring, but as yet, no such molecule has been identified. To address this issue, the present study uses high levels of electronic structure theory to compute a highly accurate quartic force field (QFF) for azirinyl cation and its two lowest lying isomers, the cyanomethyl and isocyanomethyl cations. The theoretical approach uses the singles and doubles coupled-cluster method that includes a perturbative correction for connected triple excitations, CCSD(T), together with extrapolation to the one-particle basis set limit and corrections for scalar relativity and core-correlation. The QFF is then used in a second order vibrational perturbation theory analysis (VPT2) to compute the fundamental vibrational frequencies and rovibrational spectroscopic constants for all three C2NH2+ isomers. The reliability of the VPT2 vibrational frequencies is tested by comparison to vibrational configuration interaction (VCI) calculations and excellent agreement is found between the two approaches. Fundamental vibrational frequencies and rovibrational spectroscopic constants for all singly substituted 13C, 15N, and D isotopologues are also reported. It is expected that the highly accurate spectroscopic data reported herein will be useful in the identification of these cations in high resolution experimental or astronomical observations.

Partha P Bera↗
NASA NTRS2018

Quantitative validation of Ames IR intensity and new line lists for (32/33/34)S(16)O2, (32)S(18)O2 and (16)O(32)S(18)O

The quality of Ames-296K SO2 Infrared (IR) line list intensities is first validated by quantitative exploration of several dipole moment surfaces (DMSs) and partition sum convergence. The DMSs are computed with several of Dunning’s correlation-consistent basis sets and their vibrational dependence are compared to the empirical model derived from Stark effect experiments reported by D. Patel, D. Margolese, and T.R. Dykea [J.Chem.Phys. 70, 2740 (1979)]. The effective dipole deviations from the DMS adopted in the Ames IR lists is 0.2-0.4% for vibrational states up to 3v3. The vibrational dependence of the dipole moment is also in good agreement, except for nv1. Partition sum convergence at 296K is confirmed by new calculations with rotational quantum number J up to 150 and upper state E’ up to 8000 cm-1. The isotopologue consistency of the Ames IR line lists is superior relative to the regular Effective Hamiltonian (EH) models and Effective Dipole Moment (EDM) models. The v1+v2 and v2+v3 intensity consistency check reveals the recently reported experimental intensities need significant improvement or re-analysis. After the accuracy, convergence, and isotopologue consistency have been confirmed, the theoretical Ames-296K intensities are combined with the experimental line positions or EH models that experimental spectroscopists published after 2009. Three high-resolution IR line sets are reported for the (32/33/34)S(16)O2, (32)S(18)O2 and (16)O(32)S(18)O isotopologues: (1) the “New Lines Sets” include experimentally measured line positions; (2) the “Expanded Line Sets” include possible transitions among new rovibrational levels assigned in experiments and ground state (GS) levels predicted by reliable EH models; (3) the “Ames + MARVEL Sets” include possible transitions among all those levels reported in a recent MARVEL analysis. [Tóbiás et al, JQSRT 208, 152 (2018)]. Compared to the limited data in High-resolution TRANsmission molecular absorption database (HITRAN), these line sets have significantly improved the data coverage up to 4000 cm-1. Some missing bands can be traced to the unpublished experimental data. The isotopologue consistency of these line sets will help identify the uncertainties and defects in the experimental EH and EDM models. These line sets are good candidates for the next HITRAN update, if line shape parameters are available. The line sets can be downloaded from supplementary files or from the Ames Molecular Spectroscopic Database at http://huang.seti.org.

Xinchuan Huang↗
NASA NTRSDate not supplied

Efficient Implementation for Unitary Coupled Cluster State Preparation for Near-Term Quantum Computers

Unitary coupled cluster theory (UCC) is a common wave function ansatz for quantum simulation of molecular electronic structure using the variational quantum eigenvalue solver (VQE). Even for small molecules using a double-ζ basis, the number of variational parameters required to minimize the electronic energy (i.e., optimize the circuit) is large and beyond the reach of current quantum computers. For example, a circuit simulating C2 using the UCCSD ansatz and the cc-pVDZ basis set with frozen-core will require over 10,000 variational parameters and a Hilbert space of over 10^8 determinants. To make progress on simulating such molecular systems on near-term quantum computers, we explore how much of the optimization can be approximately prepared with classical simulation while reducing the number of optimization steps performed on a quantum device. Recently, Chen, Cheng, and Freericks [J. Chem. Theory Comput. 2021, 17, 841-847] presented an algorithm for the factorized form of the UCC ansatz that allows for efficient UCC optimizations on classical hardware. We flip the algorithm around and use it to prepare approximate quantum circuits for systems that require a large number of qubits to represent. We will present results from our implementation and discuss strategies for incorporating this implementation for algorithms involving near-term quantum computers.

J Wayne Mullinax↗
NASA NTRS2022

Ames-2021 CO 2 Dipole Moment Surface and IR Line Lists: Toward 0.1% Uncertainty for CO 2 IR Intensities

A highly accurate CO 2 ab initio dipole moment surface (DMS), Ames-2021, is reported along with 12 C 16 O 2 infrared (IR) intensity comparisons approaching a 1–4‰ level of agreement and uncertainty. The Ames-2021 DMS was accurately fitted from CCSD(T) finite-field dipoles computed with the aug-cc-pVXZ (X = T, Q, 5) basis for C atom and the d-aug-cc-pVXZ (X = T, Q, 5) basis for O atoms, and extrapolated to the one particle basis set limit. Fitting σ(rms) is 3.8 × 10^(–7) au for 4443 geometries below 15 000 per cm . The corresponding IR intensity, S Ames-2021 , are computed using the Ames-2 potential energy surface (PES), which is the best PES available for CO 2 . Compared to high accuracy IR studies for 2001i–00001 and 3001i–00001 bands, S Ames-2021 matches NIST experiment-based intensities [S NIST-HIT16 or S HIT20 ] to −1.0 ± 1.3‰, or matches DLR experiment-based intensities [S DLR-HIT16/UCL/Ames ] to 1.9 ± 3.7‰. This indicates the systematic deviations and uncertainties have been significantly reduced in S Ames-2021 . The S UCL2015 (or S HITRAN2016 ) have larger deviations (vs S DLR ) and uncertainties (vs S DLR , S NIST ) which are attributed to the less accurate Ames-1 PES adopted in UCL-296 line list calculation. The S Ames-2021 intensity of 12 C 16 O 2 and 13 C 16 O 2 is utilized to derive new absolute 13 C/ 12 C ratios for Vienna PeeDee Belemnite (VPDB) with uncertainty reduced by 1/3 or 2/3. Further evaluation of S Ames-2021 are carried out on those CO 2 bands discussed in the HITRAN2020 update paper. Consistent improvements and better accuracies are found in band-by-band analysis, except for those bands strongly affected by Coriolis couplings, or very weak bands measured with relatively larger experimental uncertainties. The Ames-2021 296 K IR line lists are generated for 13 CO 2 isotopologues, with 18,000 per and S 296K > 1E–31) cm/molecule cutoff and then combined with CDSD line positions (except 14 C 16 O 2 ). The Ames-2021 DMS and 296 K IR line lists represent a major improvement over previous CO 2 theoretical IR intensity studies, including Ames-2016, UCL-296, and recent UCL DMS 2021 update. A real 1 permille level of agreement and uncertainty will definitely require both more accurate PES and more accurate DMS.

Chemical calculations↗