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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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All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Liquid Phase Modeling in Porous Media: Adsorption of Methanol and Ethanol in H-MFI in Condensed Water

Zeolites are used in the chemical and separation industries for their exceptional selectivity, adsorption capacity, regenerability, and stability in gas and liquid phase processing. Here, we developed an explicit solvation method for predicting solvent/condensed phase effects on adsorption free energies in microporous media such as zeolites based on the hybrid quantum mechanical/molecular mechanical free energy perturbation (QM/MM-FEP) technique. Our explicit solvation method for zeolite systems, called eSZS, aims to capture site-specific interactions during the adsorption process at the Brønsted acid sites of H-MFI zeolite while still considering the diverse configuration space of the solvent molecules. This strategy is ideal for chemical reactions or adsorbates that interact with the microporous medium in few distinct adsorbate/transition state configurations, i.e., the harmonic or similar approximations are acceptable for the adsorbate/transition state while such approximations break down for the solvent molecules that require extensive configuration space sampling. In this way, our approach effectively overcomes the limitations of implicit solvation models and classical force field methods for describing solvation effects on chemical reactions within porous materials such as zeolites. Specifically, in this study, we investigated various aspects of our hybrid QM/MM approach, including QM cluster size dependencies in a periodic electrostatically embedded cluster model (PEECM), rules for link atoms at the QM/MM boundary, and functional and basis set considerations for converged and reasonably accurate gas and aqueous phase methanol and ethanol adsorption free energy predictions in H-MFI. For gas phase adsorption of methanol and ethanol in H-MFI at a Brønsted acid site in T12 position, we compute adsorption free energies at 298 K of −0.61 and −0.75 eV, respectively, using a PEECM containing 50 Si and 1 Al atom with ωB97x-D/def2-TZVP level of theory. For solvent effect calculations, we sample the aqueous phase using grand canonical Monte Carlo (GCMC) simulations to (1) obtain a mean field of electrostatic interactions in the reaction system and (2) perform a rigorous free energy perturbation calculation. Similar to the experimentally and computationally observed endergonic solvation effects observed for hydrocarbon adsorption on metal surfaces, we also observe that a condensed aqueous environment destabilizes methanol and ethanol at these acid sites in H-MFI at 298 K. Specifically, the computed solvation free energies of adsorption (ΔΔG solv ) for methanol and ethanol are +0.44 and +0.54 eV, respectively. From this study, it is evident that adsorbates (methanol and ethanol) are competing with water for adsorption space inside the H-MFI zeolite, leading to an endergonic solvation effect. Here, we expect that the endergonic, aqueous solvent effect during adsorption in microporous zeolites is highly tunable by changing the pore size and hydrophobicity of the microporous material as this will affect the water density inside the pore structure.

Adsorption↗
DOE OSTI2022

Integrated Experimental and Computational K-Edge X-ray Absorption Near-Edge Structure Analysis of Vanadium Catalysts

X-ray Absorption Near-Edge Structure (XANES) spectroscopy is a powerful tool to reveal key structural and electronic features of isolated catalytic sites, yet insights into molecular structure and more detailed orbital analysis through a combination of experimental and computed XANES analysis are necessary for accurate interpretation of the spectra, especially when significant heterogeneity exits among the catalytic sites. Herein, we present an integrated computational and experimental strategy to determine both primary and secondary bonding interactions within the XANES pre-edge region for organovanadium complexes, which was developed using a series of well-defined molecular vanadium complexes and then applied to the characterization of a supported organovanadium olefin hydrogenation catalyst. Time-dependent density functional theory is used to predict the energy of pre-edge XANES features for a series of vanadium complexes with a variety of oxidation states and local coordination environments. Further, a calibration scheme incorporating different density functionals and basis sets is established, resulting in an optimized scheme that accurately predicts pre-edge energies with a mean absolute error of 0.40 eV. Second-shell coordination (e.g., V---V) effects within XANES are identified through the analysis of the computed dominant orbital contributions for multi-vanadium complexes. Orbital analysis also provided confirmation that the vanadium-hydride formation combined with the heterogeneity of the catalytic active species in ole-fin hydrogenation caused the energy shift and broadening of the pre-edge peak after hydrogen treatment of the silica-supported organovanadium pre-catalyst. This work further elucidates computational XANES simulations and techniques potentially guiding characterization in surface organometallic chemistry.

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

The Harvard organic photovoltaic dataset

Presented in this work is the Harvard Organic Photovoltaic Dataset (HOPV15), a collation of experimental photovoltaic data from the literature, and corresponding quantum-chemical calculations performed over a range of conformers, each with quantum chemical results using a variety of density functionals and basis sets. It is anticipated that this dataset will be of use in both relating electronic structure calculations to experimental observations through the generation of calibration schemes, as well as for the creation of new semi-empirical methods and the benchmarking of current and future model chemistries for organic electronic applications.

14 SOLAR ENERGY↗
DOE OSTI2016

Uncovering the lipidic basis for the preparation of functional nicotinic acetylcholine receptor detergent complexes for structural studies

This study compares the lipid composition, including individual phospholipid molecular species of solubilized nAChR detergent complexes (nAChR-DCs) with those of the bulk lipids from their source, Torpedo californica (Tc) electric tissue. This lipidomic analysis revealed seventy-seven (77) phospholipid species in the Tc tissue. Analysis of affinity-purified nAChR-DCs prepared with C-12 to C-16 phospholipid analog detergents alkylphosphocholine (FC) and lysofoscholine (LFC) demonstrated that nAChR-DCs prepared with FC12, LFC14, and LFC16 contained >60 phospholipids/nAChR, which was more than twice of those prepared with FC14, FC16, and LFC12. Significantly, all the nAChR-DCs lacked ethanolamine and anionic phospholipids, contained only four cholesterol molecules, and a limited number of phospholipid molecular species per nAChR. Upon incorporation into oocytes, FC12 produce significant functionality, whereas LFC14 and LFC16 nAChR-DCs displayed an increased functionality as compared to the crude Tc membrane. All three nAChR-DCs displayed different degrees of alterations in macroscopic activation and desensitization kinetics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Potential up-scaling of inkjet-printed devices for logical circuits in flexible electronics

Inkjet Technology is often mis-believed to be a deposition/patterning technology which is not meant for high fabrication throughput in the field of printed and flexible electronics. In this work, we report on the 1) printing, 2) fabrication yield and 3) characterization of exemplary simple devices e.g. capacitors, organic transistors etc. which are the basic building blocks for logical circuits. For this purpose, printing is performed first with a Proof of concept Inkjet printing system Dimatix Material Printer 2831 (DMP 2831) using 10 pL small print-heads and then with Dimatix Material Printer 3000 (DMP 3000) using 35 pL industrial print-heads (from Fujifilm Dimatix). Printing at DMP 3000 using industrial print-heads (in Sheet-to-sheet) paves the path towards industrialization which can be defined by printing in Roll-to-Roll format using industrial print-heads. This pavement can be termed as 'Bridging Platform'. This transfer to 'Bridging Platform' from 10 pL small print-heads to 35 pL industrial print-heads help the inkjet-printed devices to evolve on the basis of functionality and also in form of up-scaled quantities. The high printed quantities and yield of inkjet-printed devices justify the deposition reliability and potential to print circuits. This reliability is very much desired when it comes to printing of circuits e.g. inverters, ring oscillator and any other planned complex logical circuits which require devices e.g. organic transistors which needs to get connected in different staged levels. Also, the up-scaled inkjet-printed devices are characterized and they reflect a domain under which they can work to their optimal status. This status is much wanted for predicting the real device functionality and integration of them into a planned circuit.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2016

Forecasting of electronic devices lifetime on the basis of activation models of functional parameters drift

We propose a model of functional parameters drift for electronic devices, allowing predicting their lifetime. The method of model parameters estimation is developed. The developed model allows optimizing the accelerated tests modes, taking into account the complex impact of stress factors. The results are applicable for modern electronic devices with a failure rate less than 1 FIT. The results are applicable if the physical and chemical processes leading to electronic devices degradation have an activation mechanism; the activation process is due to the temperature.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2016

Vibrational spectroscopic and structural investigations on fullerene: A DFT approach

The molecular structure of fullerene (C{sub 60}) molecule was optimized by the DFT/B3LYP method with 6-31G and 6-31G(d,p) basis sets using Gaussian 09 program. The vibrational frequencies were calculated for the optimized molecular structure of the molecule. The calculated vibrational frequencies confirm that the molecular structure of the molecule was located at the minimum energy potential energy surface. The calculated vibrational frequencies were assigned on the basis of functional group analysis and also confirmed using the GaussView 05 software. The frontier molecular orbitals analysis was carried out. The FMOs related molecular properties were predicted. The higher ionization potential, higher electron affinity, higher softness, lower band gap energy and lower hardness values were obtained, which confirm that the fullerene molecule has a higher molecular reactivity. The Mulliken atomic charge distribution of the molecule was also calculated. Hence, these results play an important role due to its potential applications as drug delivery devices.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2016

A cumulant functional for static and dynamic correlation

A functional for the cumulant energy is introduced. The functional is composed of a pair-correction and static and dynamic correlation energy components. The pair-correction and static correlation energies are functionals of the natural orbitals and the occupancy transferred between near-degenerate orbital pairs, rather than the orbital occupancies themselves. The dynamic correlation energy is a functional of the statically correlated on-top two-electron density. The on-top density functional used in this study is the well-known Colle-Salvetti functional. Using the cc-pVTZ basis set, the functional effectively models the bond dissociation of H{sub 2}, LiH, and N{sub 2} with equilibrium bond lengths and dissociation energies comparable to those provided by multireference second-order perturbation theory. The performance of the cumulant functional is less impressive for HF and F{sub 2}, mainly due to an underestimation of the dynamic correlation energy by the Colle-Salvetti functional.

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

The all configuration mean energy multiconfiguration self-consistent-field method. I. Equal configuration weights

The All Configuration Mean Energy (ACME) conditions are a special case of state averaging for Multiconfigurational Self-Consistent-Field (MCSCF) orbital optimisation. The method is formulated using the Graphical Unitary Group Approach (GUGA) in which the Configuration State Function (CSF) basis is represented as walks within a Shavitt graph. This graphical formulation leads to efficient recursive algorithms for the energy and reduced density matrices (RDM) that are independent of the CSF dimension and that scale only as O(n2) where n is the number of occupied orbitals. The Hamiltonian matrix diagonalization step is obviated and the CSF expansion coefficients are neither referenced nor required. This allows MCSCF orbital optimisation to be performed for essentially unlimited numbers of active orbitals and arbitrarily large CSF expansions. The discussion includes various types of CSF expansion spaces, the partitioning of the essential and redundant orbital optimisation parameters, the computation of the spin-density, and the formulation of state-specific analytic gradients and nonadiabatic coupling for high-level electronic structure methods that use the ACME MCSCF orbitals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

Semi-microscopic model of pairing in nuclei

A semi-microscopic model for nucleon pairing in nuclei is presented starting from the ab initio BCS gap equation with the Argonne v{sub 18} force and the self-consistent energy density functional method basis characterized by the bare nucleon mass. The BCS theory is formulated in terms of the model space S{sub 0} with the effective pairing interaction calculated from the first principles in the subsidiary space S{sup '}. This effective interaction is supplemented with a small phenomenological addendum containing one phenomenological parameter, universal for all medium and heavy atomic nuclei. We consider the latter as a phenomenological way to take into account approximately both the many-body corrections to the BCS theory and the effective mass effects. For protons, the Coulomb interaction is introduced directly. Calculations made for several isotopic and isotonic chains of semi-magic nuclei are compared with empirical gap values derived from odd-even mass differences. The average disagreement is of the order of 0.1--0.2 MeV. The role of the self-consistent basis is analyzed.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2014

Purification, crystallization, preliminary X-ray diffraction and molecular-replacement studies of great cormorant (Phalacrocorax carbo) haemoglobin

The great cormorant hemoglobin has been isolated, purified and crystallized and the three dimensional structure is solved using molecular replacement technique. Haemoglobin is the iron-containing oxygen-transport metalloprotein that is present in the red blood cells of all vertebrates. In recent decades, there has been substantial interest in attempting to understand the structural basis and functional diversity of avian haemoglobins. Towards this end, purification, crystallization, preliminary X-ray diffraction and molecular-replacement studies have been carried out on cormorant (Phalacrocorax carbo) haemoglobin. Crystals were grown by the hanging-drop vapour-diffusion method using PEG 3350, NaCl and glycerol as precipitants. The crystals belonged to the trigonal system P3{sub 1}21, with unit-cell parameters a = b = 55.64, c = 153.38 Å, β = 120.00°; a complete data set was collected to a resolution of 3.5 Å. Matthews coefficient analysis indicated that the crystals contained a half-tetramer in the asymmetric unit.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2017

Efficient Scalable Parallel Higher Order Direct MoM-SIE Method With Hierarchically Semiseparable Structures for 3-D Scattering

A novel fast scalable parallel algorithm is proposed for the solution of large 3-D scattering problems based on: 1) the double (geometrical and current-approximation) higher order (DHO) method of moments (MoM) in the surface integral equation (SIE) formulation and 2) a direct solver for dense linear systems utilizing hierarchically semiseparable (HSS) structures. Namely, an HSS matrix representation is used for compression, factorization, and solution of the system matrix. In addition, a rank-revealing QR decomposition for memory compression is used, with a stopping criterion in terms of the relative rank tolerance value. One method for geometrical preprocessing of the scatterers based on the cobblestone distance sorting technique is employed in order to enhance the HSS algorithm accuracy and parallelization. Numerical examples show how the accuracy of the DHO HSS-MoM-SIE method is easily controllable by using the relative tolerance for the matrix compression. Furthermore, the examples demonstrate low memory consumption, as well as much faster simulation time, when compared to the direct LU decomposition. The method enables dramatically faster monostatic scattering computations than iterative solvers and reduced number of unknowns when compared to low-order discretizations. Finally, great scalability of the algorithm is demonstrated on more than one thousand processes.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2014

TU-F-18C-03: X-Ray Scatter Correction in Breast CT: Advances and Patient Testing

Purpose: To further develop and perform patient testing of an x-ray scatter correction algorithm for dedicated breast computed tomography (BCT). Methods: A previously proposed algorithm for x-ray scatter signal reduction in BCT imaging was modified and tested with a phantom and on patients. A wireless electronic positioner system was designed and added to the BCT system that positions a tungsten plate in and out of the x-ray beam. The interpolation used by the algorithm was replaced with a radial basis function-based algorithm, with automated exclusion of non-valid sampled points due to patient motion or other factors. A 3D adaptive noise reduction filter was also introduced to reduce the impact of scatter quantum noise post-reconstruction. The impact on image quality of the improved algorithm was evaluated using a breast phantom and seven patient breasts, using quantitative metrics such signal difference (SD) and signal difference-to-noise ratios (SDNR) and qualitatively using image profiles. Results: The improvements in the algorithm resulted in a more robust interpolation step, with no introduction of image artifacts, especially at the imaged object boundaries, which was an issue in the previous implementation. Qualitative evaluation of the reconstructed slices and corresponding profiles show excellent homogeneity of both the background and the higher density features throughout the whole imaged object, as well as increased accuracy in the Hounsfield Units (HU) values of the tissues. Profiles also demonstrate substantial increase in both SD and SDNR between glandular and adipose regions compared to both the uncorrected and system-corrected images. Conclusion: The improved scatter correction algorithm can be reliably used during patient BCT acquisitions with no introduction of artifacts, resulting in substantial improvement in image quality. Its impact on actual clinical performance needs to be evaluated in the future. Research Agreement, Koning Corp., Hologic Inc., Barco Corp Consultant Agreement, Fujifilm Medical Systems.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2019

Excited States of the dtμ, pdμ, and tpμ Mesomolecules in the Variational Method

The energy spectra of excited bound states are calculated for the muonic molecules ptμ, pdμ, and dtμ on the basis of the stochastic variational method. The basis wave functions are taken as the Gaussian in shape. The matrix elements of the Hamiltonian are calculated analytically. To perform numerical calculations, computer code is written in MATLAB. Numerical values are obtained for energies of excited P states in the muonic molecules ptμ, pdμ, and dtμ.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗