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At least 19 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS1997

Formation of Carbon Nanotube Based Gears: Quantum Chemistry and Molecular Mechanics Study of the Electrophilic Addition of o-Benzyne to Fullerenes, Graphene, and Nanotubes

Considerable progress has been made in recent years in chemical functionalization of fullerene molecules. In some cases, the predominant reaction products are different from those obtained (using the same reactants) from polycyclic aromatic hydrocarbons (PAHs). One such example is the cycloaddition of o-benzyne to C60. It is well established that benzyne adds across one of the rings in naphthalene, anthracene and other PAHs forming the [2+4] cycloaddition product (benzobicyclo[2.2.2.]-octatriene with naphthalene and triptycene with anthracene). However, Hoke et al demonstrated that the only reaction path for o-benzyne with C60 leads to the [2+2] cycloaddition product in which benzyne adds across one of the interpentagonal bonds (forming a cyclobutene ring in the process). Either reaction product results in a loss of aromaticity and distortion of the PAH or fullerene substrate, and in a loss of strain in the benzyne. It is not clear, however, why different products are preferred in these cases. In the current paper, we consider the stability of benzyne-nanotube adducts and the ability of Brenner's potential energy model to describe the structure and stability of these adducts. The Brenner potential has been widely used for describing diamondoid and graphitic carbon. Recently it has also been used for molecular mechanics and molecular dynamics simulations of fullerenes and nanotubes. However, it has not been tested for the case of functionalized fullerenes (especially with highly strained geometries). We use the Brenner potential for our companion nanogear simulations and believe that it should be calibrated to insure that those simulations are physically reasonable. In the present work, Density Functional theory (DFT) calculations are used to determine the preferred geometric structures and energetics for this calibration. The DFT method is a kind of ab initio quantum chemistry method for determining the electronic structure of molecules. For a given basis set expansion, it is comparable in accuracy to the MP2 method (better than Hartree Fock, but less accurate than more extensive electron correlation methods such as MP4 or CCSD). However, for systems with large numbers of basis functions it more efficient than any other methods that include electron correlation effects. In this presentation we show the results of DFT calculations for the reaction of benzyne with naphthalene, C60, and nanotube models. We compare energies for [2+2] and [2+4] cycloaddition products. The preferred products for the naphthalene and C60 reactions have been determined by experiment and, thus, these cases serve as a validation of our quantum chemical approach. We also compare the DFT and Brenner potential results. Finally we can predict the likelihood of reaction between benzyne and nanotubes.

Jaffe, Richard↗
NASA NTRS2023

Cavity Ring-Down Spectroscopy of Anthracene, 9-Methylanthracene, and 2 Methylanthracene in Supersonic Expansion

The S0–S1 absorption spectra of anthracene (C14H10), 9-methylanthracene (C15H12), and 2-methylanthracene (C15H12) are measured in the ultraviolet region between 330 and 375 nm (26,666 to 30,303 cm–1) with cavity ring-down spectroscopy in supersonic free-jet expansions of argon. The associated vibronic band systems and their spectroscopic assignments are discussed and compared to previous studies performed using fluorescence excitation and dispersed fluorescence techniques. Density functional theory (DFT) calculations were carried out to study the structures and evaluate the vibrational transitions of the ground and excited states. Time-dependent DFT calculations of the first electronic excited states and Franck–Condon factor calculations were carried out to assist in the assignment of the experimentally measured vibronic bands. The vibronic spectra obtained in absorption agree well with fluorescence excitation spectra in terms of peak positions but exhibit different relative band intensities. We find a very good match between experimentally obtained vibronic line positions and the peak positions of the quantum chemically calculated Franck–Condon excitation lines.

Salma Bejaoui↗
NASA NTRS2004

Theoretical Investigation of OCN(-) Charge Transfer Complexes in Condensed Phase Media: Spectroscopic Properties in Amorphous Ice

Density functional theory (DFT) calculations of cyanate (OCN(-)) charge-transfer complexes were performed to model the "XCN" feature observed in interstellar icy grain mantles. OCN(-) charge-transfer complexes were formed from precursor combinations of HNCO or HOCN with either NH3 or H2O. Three different solvation strategies for realistically modeling the ice matrix environment were explored, including (1) continuum solvation, (2) pure DFT cluster calculations, and (3) an ONIOM DFT/PM3 cluster calculation. The model complexes were evaluated by their ability to reproduce seven spectroscopic measurements associated with XCN: the band origin of the OCN(-) asymmetric stretching mode, shifts in that frequency due to isotopic substitutions of C, N, O, and H, plus two weak features. The continuum solvent field method produced results consistent with some of the experimental data but failed to account for other behavior due to its limited capacity to describe molecular interactions with solvent. DFT cluster calculations successfully reproduced the available spectroscopic measurements very well. In particular, the deuterium shift showed excellent agreement in complexes where OCN(-) was fully solvated. Detailed studies of representative complexes including from two to twelve water molecules allowed the exploration of various possible solvation structures and provided insights into solvation trends. Moreover, complexes arising from cyanic or isocyanic acid in pure water suggested an alternative mechanism for the formation of OCN(-) charge-transfer complexes without the need for a strong base such as NH3 to be present. An extended ONIOM (B3LYP/PM3) cluster calculation was also performed to assess the impact of a more realistic environment on HNCO dissociation in pure water.

Park, Jin-Young↗
NASA NTRS2009

Discrete Fourier Transform Analysis in a Complex Vector Space

Alternative computational strategies for the Discrete Fourier Transform (DFT) have been developed using analysis of geometric manifolds. This approach provides a general framework for performing DFT calculations, and suggests a more efficient implementation of the DFT for applications using iterative transform methods, particularly phase retrieval. The DFT can thus be implemented using fewer operations when compared to the usual DFT counterpart. The software decreases the run time of the DFT in certain applications such as phase retrieval that iteratively call the DFT function. The algorithm exploits a special computational approach based on analysis of the DFT as a transformation in a complex vector space. As such, this approach has the potential to realize a DFT computation that approaches N operations versus Nlog(N) operations for the equivalent Fast Fourier Transform (FFT) calculation.

Dean, Bruce H.↗
NASA NTRS2013

Association Mechanisms of Unsaturated C2 Hydrocarbons with Their Cations: Acetylene and Ethylene

The ion-molecule association mechanism of acetylene and ethylene with their cations is investigated by ab initio quantum chemical methods to understand the structures, association energies, and the vibrational and electronic spectra of the products. Stable puckered cyclic isomers are found as the result of first forming less stable linear and bridge isomers. The puckered cyclic complexes are calculated to be strongly bound, by 87, 35 and 56 kcal/mol for acetylene-acetylene cation, ethylene-ethylene cation and acetylene-ethylene cation, respectively. These stable complexes may be intermediates that participate in further association reactions. There are no association barriers, and no significant inter-conversion barriers, so the initial linear and bridge encounter complexes are unlikely to be observable. However, the energy gap between the bridged and cyclic puckered isomers greatly differs from complex to complex: it is 44 kcal/mol in C4H4 +, but only 6 kcal/mol in C4H8 +. The accurate CCSD(T) calculations summarized above are also compared against less computationally expensive MP2 and density functional theory (DFT) calculations for structures, relative energies, and vibrational spectra. Calculated vibrational spectra are compared against available experiments for cyclobutadiene cation. Electronic spectra are also calculated using time-dependent DFT.

ethylene↗
NASA NTRSDate not supplied

Does Chirality Influence the Stability of Amino Acid –Cu Complexes in the Salt-Induced Peptide Formation Reaction? Insights from Density Functional Theory Calculations

The polymerization of amino acids into peptides and ultimately proteins is critical to evolution of life. Ribosomally-synthesized proteins are homochiral, composed entirely of L-amino acids. Abiotic syntheses of amino acids, however, produce racemic mixtures(equal amounts of L and D enantiomers), meaning that the pool of monomers available for abiotic protein synthesis would be racemic or nearly so. There are no prebiotically plausible mechanisms known to yield homochiral peptides from racemic pools of amino acids. While some mechanisms capable of producing or amplifying enantiomeric excesses have been observed, these excesses are small or not applicable to all biologically relevant amino acids. As a result, a prebiotically-feasible mechanism to create enantiopure pools of amino acids has not been identified. However, it is not clear that these enantio-enriched or enantiopure pools are necessary to produce homochiral peptides. Steric and electronic effects, or a combination of both, may influence how different enantiomers interact with each other, potentially leading to homochiral peptides from racemic mixtures. Here, we use density functional theory (DFT) calculations to assess the stability of homochiral and heterochiral reactive complexes produced during polymerization via the salt-induced peptide formation (SIPF) reaction. Experimental studies of the SIPF reaction have shown that it enables the formation of peptides under diverse environmental conditions, making it a plausible pathway to peptide formation on early Earth. In the SIPF reaction, NaCl acts as a condensation reagent while a divalent metal cation, primarily Cu2+, facilitates polymerization by complexing and activating amino acids forming a monochlorocuprate complex. To assess if hetero-or homochiral monochlorocuprate complexes were energetically favored, we compared the stability of LL, DD, and LD enantiomers of Cu2+–(alanine)2and Cu2+–(valine) 2 complexes. Gaussian 09 density DFT energy-minimization calculations were made for each Cu –amino acid complex in the cis and trans configuration. Models were energy minimized using the BH and HLYP/6-31++G(d,p) level of theory and free energies were compared to determine the most stable configuration.

A C Fox↗
NASA NTRS2015

Discrete Fourier Transform in a Complex Vector Space

An image-based phase retrieval technique has been developed that can be used on board a space based iterative transformation system. Image-based wavefront sensing is computationally demanding due to the floating-point nature of the process. The discrete Fourier transform (DFT) calculation is presented in "diagonal" form. By diagonal we mean that a transformation of basis is introduced by an application of the similarity transform of linear algebra. The current method exploits the diagonal structure of the DFT in a special way, particularly when parts of the calculation do not have to be repeated at each iteration to converge to an acceptable solution in order to focus an image.

Dean, Bruce H.↗
NASA NTRS1997

The Vibrational Frequencies of CaO2, ScO2, and TiO2: A Comparison of Theoretical Methods

The vibrational frequencies of several states of CaO2, ScO2, and TiO2 are computed at using density functional theory (DFT), the Hatree-Fock approach, second order Moller-Plesset perturbation theory (MP2), and the complete-active-space self-consistent-field theory. Three different functionals are used in the DFT calculations, including two hybrid functionals. The coupled cluster singles and doubles approach including the effect of unlinked triples, determined using perturbation theory, is applied to selected states. The Becke-Perdew 86 functional appears to be the cost effective method of choice, although even this functional does not perform well for one state of CaO2. The MP2 approach is significantly inferior to the DFT approaches.

Rosi, Marzio↗
NASA NTRS2004

Adaptive DFT-based Interferometer Fringe Tracking

An automatic interferometer fringe tracking system has been developed, implemented, and tested at the Infrared Optical Telescope Array (IOTA) observatory at Mt. Hopkins, Arizona. The system can minimize the optical path differences (OPDs) for all three baselines of the Michelson stellar interferometer at IOTA. Based on sliding window discrete Fourier transform (DFT) calculations that were optimized for computational efficiency and robustness to atmospheric disturbances, the algorithm has also been tested extensively on off-line data. Implemented in ANSI C on the 266 MHz PowerPC processor running the VxWorks real-time operating system, the algorithm runs in approximately 2.0 milliseconds per scan (including all three interferograms), using the science camera and piezo scanners to measure and correct the OPDs. The adaptive DFT-based tracking algorithm should be applicable to other systems where there is a need to detect or track a signal with an approximately constant-frequency carrier pulse.

Wilson, Edward↗
NASA NTRS2004

Photoionization of Benzene and Small Polycyclic Aromatic Hydrocarbons in Ultraviolet-Processed Astrophysical Ices: A Computational Study

We employed density functional theory (DFT) calculations to model the photoionization behavior of benzene and small polycyclic aromatic hydrocarbons when they are embedded in a matrix of water ice in order to investigate issues raised by recent experimental work by Gudipati and Allamandola. The ionization energies of benzene, naphthalene, anthracene, and pyrene were found to be lowered by 1.5-2.1 eV in water ice. Low-lying vertical electronic excitation energies were computed with time-dependent DFT for both neutral and ionized species and are found in both cases to be remarkably unaffected by the ice matrix. Chemical behavior in ultraviolet-photoprocessed ices is also discussed, with a focus on electron recombination and pathways leading to phenol and analogous products.

Woon, D. E.↗
NASA NTRS1996

Theoretical Chemistry At NASA Ames Research Center

The theoretical work being carried out in the Computational Chemistry Branch at NASA Ames will be overviewed. This overview will be followed by a more in-depth discussion of our theoretical work to determine molecular opacities for the TiO and water molecules and a discussion of our density function theory (DFT) calculations to determine the harmonic frequencies and intensities to the vibrational bands of polycyclic aromatic hydrocarbons (PAHs) to assess their role as carriers to the unidentified infrared (UIR) bands. Finally, a more in-depth discussion of our work in the area of computational molecular nanotechnology will be presented.

Langhoff, Stephen↗
NASA NTRS1997

Quantum Chemistry Study of Cycloaddition Pathways for the Reaction of o-Benzyne with Fullerenes and Carbon Nanotubes

Functionalization of fullerenes via the [2+2] cycloaddition reaction with o-benzyne has been demonstrated in the laboratory. In contrast, [2+4) cycloaddition products are formed when benzyne reacts with planar polycyclic aromatic hydrocarbons. Using density functional theory (DFT) calculations with Becke's hybrid functional and small contracted gaussian basis sets, we are able to reproduce these product preferences. The objective of this work is to explore the functionalization of carbon nanotubes. We have studied o-benzyne cycloaddition products with a [14,0] single-walled nanotube. We find both the [2+2] and [2+4] adducts to be stable, with the latter product being somewhat favored.

Jaffe, Richard↗
NASA NTRS2004

Adaptive DIT-Based Fringe Tracking and Prediction at IOTA

An automatic fringe tracking system has been developed and implemented at the Infrared Optical Telescope Array (IOTA). In testing during May 2002, the system successfully minimized the optical path differences (OPDs) for all three baselines at IOTA. Based on sliding window discrete Fourier transform (DFT) calculations that were optimized for computational efficiency and robustness to atmospheric disturbances, the algorithm has also been tested extensively on off-line data. Implemented in ANSI C on the 266 MHZ PowerPC processor running the VxWorks real-time operating system, the algorithm runs in approximately 2.0 milliseconds per scan (including all three interferograms), using the science camera and piezo scanners to measure and correct the OPDs. Preliminary analysis on an extension of this algorithm indicates a potential for predictive tracking, although at present, real-time implementation of this extension would require significantly more computational capacity.

Wilson, Edward↗
NASA NTRS1995

Using Density Functional Theory (DFT) for the Calculation of Atomization Energies

The calculation of atomization energies using density functional theory (DFT), using the B3LYP hybrid functional, is reported. The sensitivity of the atomization energy to basis set is studied and compared with the coupled cluster singles and doubles approach with a perturbational estimate of the triples (CCSD(T)). Merging the B3LYP results with the G2(MP2) approach is also considered. It is found that replacing the geometry optimization and calculation of the zero-point energy by the analogous quantities computed using the B3LYP approach reduces the maximum error in the G2(MP2) approach. In addition to the 55 G2 atomization energies, some results for transition metal containing systems will also be presented.

Bauschlicher, Charles W., Jr.↗
NASA NTRSDate not supplied

A Machine Learning-Derived Atomistic Potential for Y2Si2O7

Incorporation of SiC/SiC ceramic matrix composite (CMC) hot section components into aircraft engines promises to increase efficiency and safety. However, SiC/SiC CMCs are subject to water vapor-induced oxidation and recession at the high temperatures of engine operation, and thus environmental barrier coatings (EBCs) are required to reduce this degradation and enable their widespread adoption. An understanding of EBCs failure mechanisms, including thermochemical and thermomechanical mechanisms, is essential as coating degradation leads to reduced CMC component service life. Computational modeling approaches can provide insight into EBC material properties important for coating design. However, density functional theory (DFT) is computationally expensive and atomistic potentials are lacking for materials of interest. In this work, we utilize a machine learning approach and DFT training data to parameterize atomistic potentials for two candidate EBC materials, Y2Si2O7 and Yb2Si2O7. These potentials enable near DFT-accurate calculations of thermodynamic and thermomechanical properties essential to EBC design.

Cameron J Bodenschatz↗
NASA NTRS1997

Comparison of DFT with Traditional Methods for the Calculation of Vibrational Frequencies and Bond Energies

The vibrational frequencies of MO2 are computed at many levels of theory, including HF, B3LYP, BP86, CASSCF, MP2, and CCSD(T). The computed results are compared with the available experimental results. Most of the methods fail for at least one state of the systems considered. The accuracy of the results and the origin of the observed failures are discussed. The B3LYP bond energies are compared with traditional methods for a variety of systems, ranging from FeCOn+ to SiCln and its positive ions. The cases where B3LYP differs from the traditional methods are discussed.

Bauschlicher, Charles W.↗
NASA NTRSDate not supplied

Machine Learning Approaches for Rare-Earth Silicate Environmental Barrier Coating Thermochemical and Thermomechanical Property Predictions

Environmental barrier coatings (EBCs) are a necessary enabling technology for the transition from superalloys to silicon carbide (SiC) ceramic matrix composites (CMCs) in gas turbine engines for increased efficiency and decreased fuel costs. SiC-based CMCs are prone to oxidation-based degradation in the engine hot section, and rare-earth (RE) silicates are promising candidates for EBCs due to their close thermal expansion match to the composite substrate and oxidation resistance. However, the design of EBCs is hindered by the large chemical space of candidate materials and the difficulty in obtaining material properties for engineering optimization. This is especially difficult as research continues into mixed-cation or “high-entropy” RE silicates. First-principles computational methods such as density functional theory (DFT) are highly effective at calculating material properties to guide coating design but are limited by their computational cost. Atomistic simulations have the potential to both accelerate property calculations and expand the properties able to be calculated due to their lower computational compared to DFT. However, they require interatomic potentials (IAPs) specific to the material system of interest, and, to our knowledge, there are no suitable IAPs for RE silicates. Machine learning (ML) is a promising technique to accelerate material property predictions indirectly by generating IAPs for atomistic simulations or via direct prediction. In this work, we present two ML approaches to accelerate the calculation of RE silicate properties relevant to EBC design: 1) a ML-derived interatomic potential (IAP) for atomistic simulations of yttrium disilicate (Y2Si2O7) from DFT training data, and 2) a neural network (NN) model to directly predict thermochemical properties of RE silicates and oxides directly from easily obtainable unit cell parameters. Classical MD simulations using the IAP yield lattice properties and bond lengths in good agreement with both DFT and experimental results from x-ray diffraction. Thermodynamic properties calculated using the finite-displacement phonon method and quasi-harmonic approximation were orders of magnitude faster than DFT with good agreement to the DFT results. The IAP was also used to calculate properties such as coefficient of thermal expansion (CTE) that require large simulation supercells and are therefore difficult with DFT. The IAP correctly predicted the anisotropic nature of the CTE in three different phases of Y2Si2O7. The NN model predicts constant pressure heat capacity, Cp, orders of magnitude faster than DFT calculations, which can enable its use as a surrogate model for multiscale simulations. The two methods presented in this work demonstrate the utility of ML for accelerating the prediction of RE silicate properties, which can in turn accelerate EBC design and optimization.

machine learning↗
NASA NTRS1986

VLSI Architectures for Computing DFT's

Simplifications result from use of residue Fermat number systems. System of finite arithmetic over residue Fermat number systems enables calculation of discrete Fourier transform (DFT) of series of complex numbers with reduced number of multiplications. Computer architectures based on approach suitable for design of very-large-scale integrated (VLSI) circuits for computing DFT's. General approach not limited to DFT's; Applicable to decoding of error-correcting codes and other transform calculations. System readily implemented in VLSI.

Truong, T. K.↗