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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 OSTI2022

Development and application of ReaxFF methodology for understanding the chemical dynamics of metal carbonates in aqueous solutions

A new ReaxFF reactive force field has been developed for metal carbonate systems including Na + , Ca 2+ , and Mg 2+ cations and the CO 3 2– anion. This force field is fully transferable with previous ReaxFF water and water/electrolyte descriptions. The Me–O–C (Me = metal) three-body valence angle parameters and Me–C non-reactive parameters of the force field have been optimized against quantum mechanical calculations including equations of state, heats of formation, heats of reaction, angle distortions and vibrational frequencies. The new metal carbonate force field has been validated using molecular dynamics simulations to study the solvation and reactivity of metal and carbonate ions in water at 300 K and 700 K. The coordination radius and self-diffusion coefficient show good consistency with existing experimental and simulation results. The angular distribution analysis explains the structural preference of carbonate ions to form carbonates and bicarbonates, where Na + predominantly forms carbonates due to weaker angular strain, while Ca 2+ and Mg 2+ prefer to form bicarbonate monodentate in nature. Residence time distribution analyses on different systems reveal the role of ions in accelerating and decelerating the dynamics of water and carbonate ions under different thermodynamic conditions. The formation and dissolution of bicarbonates and carbonates in solution were explored on the basis of the protonation capability in different systems. Here, the nucleation phenomenon of metal carbonates at ambient and supercritical conditions is explained from the perspective of cluster formation over time: Ca 2+ ions can form prenucleation clusters at ambient temperature but show saturation with increasing temperature, whereas Na + and Mg 2+ ions show a rapid increase in cluster size and amount upon increasing time and temperature.

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

Halogenated PETN derivatives: interplay between physical and chemical factors in explosive sensitivity

Determining the factors that influence and can help predict energetic material sensitivity has long been a challenge in the explosives community. Decades of literature reports identify a multitude of factors both chemical and physical that influence explosive sensitivity; however no unifying theory has been observed. Recent work by our team has demonstrated that the kinetics of “trigger linkages” (i.e., the weakest bonds in the energetic material) showed strong correlations with experimental drop hammer impact sensitivity. These correlations suggest that the simple kinetics of the first bonds to break are good indicators for the reactivity observed in simple handling sensitivity tests. Herein we report the synthesis of derivatives of the explosive pentaerythritol tetranitrate (PETN) in which one, two or three of the nitrate ester functional groups are substituted with an inert group. Experimental and computational studies show that explosive sensitivity correlates well with Q (heat of explosion), due to the change in the number of trigger linkages removed from the starting material. In addition, this correlation appears more significant than other observed chemical or physical effects imparted on the material by different inert functional groups, such as heat of formation, heat of explosion, heat capacity, oxygen balance, and the crystal structure of the material.

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

The energetics and dynamics of confinement in flexible frameworks and molecular confinement

Porous frameworks form the chemical and structural basis for critical technologies in separations, catalysis, nuclear waste containment and biomedical applications. Hundreds of zeolites and metal organic frameworks (MOFs) have been synthesized, and their ability to separate and store hydrogen, methane and carbon dioxide has been investigated both experimentally and theoretically. Nevertheless, a fundamental and systematic molecular-level understanding of the thermodynamic and structural factors governing the stability and guest-host interactions in these materials lags behind focused studies of specific systems. Because the guest molecules interact with each other and with the host framework, molecular confinement is a finely balanced and complex phenomenon. The ability of the guest molecules to bind and diffuse through the pores is determined by the nature of the host framework which, in turn, responds to the nature and concentration of guest molecules and to pressure and temperature. The work explores how framework flexibility, tailored by structure, composition, temperature and pressure, is a general phenomenon, similar in nature but variable in extent, in both zeolites and MOFs and is part of a free energy landscape in which framework-guest interactions, pressure, and temperature result in changes in framework geometry and, in some cases, phase transitions. These subtle and/or pronounced changes in lattice geometry, energetics, and dynamics can play a decisive role in confinement and in differentiating the binding of molecules of similar size. The free energy landscape created by these structural changes links polymorphism, amorphization, “breathing,” “gate opening” and confinement. Specifically, the generality of such behavior arises from commonalities in lattice dynamics and energetics of frameworks containing a combination of strong rigid bonds and weaker more flexible deformation modes. Identifying and describing these common and collective phenomena is the focus of the research on a selected group of zeolites and MOFs. Structural studies using X-ray and neutron diffraction explore the mechanical functionality of these important materials, specifically how framework materials respond to changes in temperature, pressure and guest loading. These structural studies are combined with calorimetric measurements, using techniques uniquely developed in the participating laboratories, of heats of formation, heat capacities and entropies, and guest-host interactions. The experimental thermodynamic studies are complemented by inelastic neutron scattering studies of the lattice dynamics related both to framework vibrations and to guest-host interactions. The report below summarizes the work done at UC Davis, which is complemented by work done at BYU (Woodfield) and Virginia Tech (Ross).

36 MATERIALS SCIENCE↗
DOE OSTI2022

The energetics and dynamics of confinement in flexible frameworks and molecular confinement

Porous frameworks form the chemical and structural basis for critical technologies in separations, catalysis, nuclear waste containment and biomedical applications. Hundreds of zeolites and metal organic frameworks (MOFs) have been synthesized, and their ability to separate and store hydrogen, methane and carbon dioxide has been investigated both experimentally and theoretically. Nevertheless, a fundamental and systematic molecular-level understanding of the thermodynamic and structural factors governing the stability and guest-host interactions in these materials lags behind focused studies of specific systems. Because the guest molecules interact with each other and with the host framework, molecular confinement is a finely balanced and complex phenomenon. The ability of the guest molecules to bind and diffuse through the pores is determined by the nature of the host framework which, in turn, responds to the nature and concentration of guest molecules and to pressure and temperature. The work explores how framework flexibility, tailored by structure, composition, temperature and pressure, is a general phenomenon, similar in nature but variable in extent, in both zeolites and MOFs and is part of a free energy landscape in which framework-guest interactions, pressure, and temperature result in changes in framework geometry and, in some cases, phase transitions. These subtle and/or pronounced changes in lattice geometry, energetics, and dynamics can play a decisive role in confinement and in differentiating the binding of molecules of similar size. The free energy landscape created by these structural changes links polymorphism, amorphization, “breathing,” “gate opening” and confinement. Specifically, the generality of such behavior arises from commonalities in lattice dynamics and energetics of frameworks containing a combination of strong rigid bonds and weaker more flexible deformation modes. Identifying and describing these common and collective phenomena is the focus of the research on a selected group of zeolites and MOFs. Structural studies using X-ray and neutron diffraction explore the mechanical functionality of these important materials, specifically how framework materials respond to changes in temperature, pressure and guest loading. These structural studies are combined with calorimetric measurements, using techniques uniquely developed in the participating laboratories, of heats of formation, heat capacities and entropies, and guest-host interactions. The experimental thermodynamic studies are complemented by inelastic neutron scattering studies of the lattice dynamics related both to framework vibrations and to guest-host interactions. This research was a collaboration between UC Davis (A. Navrotsky) BYU (B. Woodfield) and Virginia Tech (N. Ross).

36 MATERIALS SCIENCE↗
NASA NTRS1968

Twin solution calorimeter determines heats of formation of alloys at high temperatures

Calvert-type, twin liquid metal solution calorimeter determines the heats of formation of transition metal alloys at high temperatures. The twin differential calorimeter measures the small heat effects generated over extended periods of time, has maximum operating temperature of 1073 degrees K and an automatic data recording system.

Darby, J. B., Jr.↗
NASA NTRS1994

Heat of formation determination of the ground and excited state of cyanomethylene (HCCN) radical

Ab initio electronic structure theory has been used to characterize the structure of the ground triplet and lowest singlet excited states of cyanomethylene. The geometries, vibrational frequencies, and heats of formation have been determined using second-order Moller-Plesset perturbation, single and double excitation configuration interaction, and quadratic configuration interaction theory. The heat of formation is predicted with isodesmic reaction and Gaussian-2 theory (G2) for the ground triplet and first excited singlet states of cyanomethylene. For the ground state Delta-H(sub 0)(sup f,0) is 114.8+/-2 kcal/mol while for the excited single state it is 126.5+/-2 kcal/mol.

Francisco, Joseph S.↗
NASA NTRS1997

Temperature-Dependent Kinetics Studies of the Reactions Br((sup 2)P(sub 3/2)) + CH3SCH3 reversible reaction CH3SCH2 + HBr. Heat of Formation of the CH3SCH2 Radical

Time-resolved resonance fluorescence detection of Br((sup 2)P(sub 3/2)) atom disappearance or appearance 266 nm laser flash photolysis of CF2Br2/CH3SCH3/H2/N2 and Cl2CO/CH2SCH3/HBr/H2/N2 mixtures has been employed to study the kinetics of the reactions Br((sup 2)P(sub 3/2)) + CH3SCH3 reversible reaction HBr + CH3SCH2 (1,-1) as a function of temperature over the range 386-604 K. Arrhenius expressions in units of cu cm/molecule which describe the results are k3= (9.0 +/- 2.9) x 10 (exp -11) exp[(-2386 +/- 151)/T]; errors are 2 sigma and represent precision only. To our knowledge, these are the first kinetic data reported for each of the two reactions studied. Second and third law analyses of the equilibrium data for reactions 1 and -1 have been employed to obtain the following enthalpies of reaction in units of kcal/mol: Delta-H(298) = 6.11 +/- 1.37 and Delta-H(0) = 5.37 +/- 1.38. Combining the above enthalpies of reaction with the well-known heats of formation of Br, HBr, CH3SCH3 gives the following heats of formation of the CH3SCH2 radical in units of kcal/mol: Delta-H(sub(f,298)) = 32.7 +/- 1.4 and Delta-H(sub (f,0)) = 35.3 +/- 1.4; errors are 2 sigma and represent estimates of absolute accuracy. The C-H bond dissociation energy in CH3SCH3 obtained from our data, 93.7 +/- 1.4 kcal/mol at 298 K and 92.0 +/- 1.4 kcal at 0 k, agrees well with a recent molecular beam photofragmentaion study but is 3 kcal/mol lower than the value obtained from an iodination kinetics study.

Jefferson, A.↗
DOE OSTI2025

Numerical simulation of frost formation and heat transfer on fin-and-tube heat exchangers in turbulent cross-flow

Frost formation in fin-and-tube heat exchangers in turbulent cross-flow presents significant challenges in industrial refrigeration applications, affecting heat transfer efficiency and operational reliability. The purpose of this work is to investigate frost deposition and growth on a staggered bank of a fin-and-tube freezer coil under turbulent forced convection conditions. The focus here is on investigating conditions that closely replicate real-world scenarios in large walk-in industrial freezers. Using a direct numerical simulation approach, we examine the flow dynamics and thermal behaviour in the presence of frost, considering turbulent regimes characterized by a Reynolds number in the range 1050 ≤ R e D , avg ≤ 4800 , with the characteristic length being the outer diameter of the tube and the velocity being the bulk fluid velocity between the plates (fins). Computational fluid dynamics simulations are employed to resolve the interactions between turbulent airflow and the frost layer. Our approach incorporates a modified immersed boundary method and a slow-time acceleration technique to address the complex dynamic interface between the continuously evolving frost layer and the flowing air stream. Our findings indicate that frost forms more on the sides of the finned surfaces (plates) and less on the tubes themselves. This article is part of the theme issue ‘Heat and mass transfer in frost and ice’.

Science & Technology - Other Topics↗
DOE OSTI2023

Coupled Cluster Study of the Heats of Formation of UF 6 and the Uranium Oxyhalides, UO 2 X 2 (X = F, Cl, Br, I, and At)

The atomization enthalpies of the U(VI) species UF6 and the uranium oxyhalides UO 2 X 2 (X=F, Cl, Br, I, At) were calculated using a composite relativistic Feller-Peterson-Dixon (FPD) approach based on scalar relativistic DKH3-CCSD(T) with extrapolations to the CBS limit. The inherent multideterminantal nature of the U atom was mitigated by utilizing the singly charged atomic cation in all calculations with correction back to the neutral asymptote via the accurate ionization energy of the U atom. The effects of SO coupling were recovered using full 4-component CCSD(T) with contributions due to the Gaunt Hamiltonian calculated using Dirac-Hartree-Fock. The final atomization enthalpy for UF 6 (752.2 kcal/mol) was within 2.5 kcal/mol of the experimental value, but unfortunately the latter carries a ±2.4 kcal/mol uncertainty that is predominantly due to the experimental uncertainty in the formation enthalpy of U atom. The analogous value for UO 2 F 2 (607.6 kcal/mol) was in nearly exact agreement with experiment, but the latter has a stated experimental uncertainty of ±4.3 kcal/mol. The FPD atomization enthalpy for UO 2 Cl 2 (540.4 kcal/mol) was within the experimental error limits of ±5.5 kcal/mol. FPD atomization energies for the non-U-containing molecules (used for reaction enthalpies) H 2 O and HX (X=F, Cl, Br, I, At) were within at most 0.3 kcal/mol of their experimental values where available. The FPD atomization enthalpies, together with FPD reaction enthalpies for two different reactions, were used to determine heats of formation for all species of this work with estimated uncertainties of ±4 kcal/mol. The calculated heat of formation for UF 6 (-511.0 kcal/mol) is within 2.5 kcal/mol of the accurately-known (±0.45 kcal/mol) experimental value.

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

Prediction of the structures and heats of formation of MO 2 , MO 3 , and M 2 O 5 for M = V, Nb, Ta, Pa

Structures for the mono-, di-, and tri-bridge isomers of M 2 O 5 as well as those for the MO 2 and MO 3 fragments for M = V, Nb, Ta, and Pa were optimized at the density functional theory (DFT) level. Single point CCSD(T) calculations extrapolated to the complete basis set (CBS) limit at the DFT geometries were used to predict the energetics. Here, the lowest energy dimer isomer was the di-bridge for M = V and Nb and the tri-bridge for M = Ta and Pa. The di-bridge isomers were predicted to be composed of MO 2 + and MO 3 - fragments, whereas the mono- and tri-bridge are two MO 2 + fragments linked by an O 2 - . The heats of formation of M 2 O 5 dimers, as well as MO 2 and MO 3 neutral and ionic species were predicted using the Feller–Peterson–Dixon (FPD) approach. The heats of formation of the MF 5 species were calculated to provide additional benchmarks. Dimerization energies to form the M 2 O 5 dimers are predicted to become more negative going down group 5 and range from -29 to -45 kcal mol -1 . The ionization energies (IEs) for VO 2 and TaO 2 are essentially the same at 8.75 eV whereas the IEs for NbO 2 and PaO 2 are 8.10 and 6.25 eV, respectively. The predicted adiabatic electron affinities (AEAs) range from 3.75 eV to 4.45 eV for the MO 3 species and vertical detachment energies from 4.21 to 4.59 eV for MO 3 - . The calculated M[double bond, length as m-dash]O bond dissociation energies increase from 143 kcal mol -1 for M = V to ~170 kcal mol -1 for M = Nb and Ta to ~200 kcal mol -1 for M = Pa. The M–O bond dissociation energies are all similar ranging from 97 to 107 kcal mol -1 . Natural bond analysis provided insights into the types of chemical bonds in terms of their ionic character. Pa 2 O 5 is predicted to behave like an actinyl species dominated by the interactions of approximately linear PaO 2 + groups.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1982

Heats of formation and thermodynamic functions for C2H, C3H, and C4H from 300 K to 6000 K

A review of the energy level and heat of formation data for the species C2H, C3H, and C4H is given. The procedure for computing thermochemical data from partition function is also reviewed. Working expressions for approximate partition functions, free-energy function, enthalpy function, and heat capacity for a linear polyatomic species are presented.

Saturno, A. F.↗
NASA NTRS1995

The Heat of Formation of HNO

The HNO molecule is of interest in both combustion and atmospheric chemistry. For example, Guadagnini et al. have recently presented ab initio potential energy surfaces for the three lowest lying electronic states of HNO and then used these in examining several chemical reactions that take place in the combustion of nitrogen containing fuels and in the oxidation of atmospheric nitrogen. We have previously studied the ground state potential energy surface (i.e., stationary points along the HNO rev. reaction HON path), vibrational spectrum (using an accurate quartic force field), zero-point energy, and bonding of HNO using coupled-cluster ab initio methods. HNO is also very interesting because of the unique nature of its bonding characteristics. That is, the potential energy surface is very flat along the H-N bonding coordinate thereby giving unusual harmonic and fundamental vibrational frequencies, and the H-N bond energy is rather weak in comparison to other H-N bond energies. In fact, using experimental heats of formation for HO, H, and NO, the H- bond energy is computed to be only 49.9 kcal/ mol (298 K). However, ab initio calculations of isodesmic reaction energies involving HNO, FNO, ClNO, and several other molecules have shown that there is an inconsistency in the experimental heats of formation of the XNO (X=H, F, and Cl) species. Hence the motivation for this study was to determine a very accurate(DELTA)H(sup o)(sub f) value for HNO using state of-the-art ab initio methods. Based on many recent studies it is evident that the singles and doubles coupled-cluster method that includes a perturbational estimate of the effects of connected triple excitations, denoted CCSD(T), in conjunction with large one-particle basis sets should be reliable to better than +0.8 kcal/mol for this quantity. The computational methodology is described in the next section followed by our results and discussion. Conclusions are presented in the final section.

Lee, Timothy J.↗
NASA NTRS1995

The Heat of Formation of HNO

The HNO molecule is of interest in both combustion and atmospheric chemistry. For example, Guadagnini et al. have recently presented ab initio potential energy surfaces for the three lowest lying electronic states of HNO and then used these in examining several chemical reactions that take place in the combustion of nitrogen containing fuels and in the oxidation of atmospheric nitrogen. We have previously studied the ground state potential energy surface (i.e., stationary points along the HNO reversible reaction HON path), vibrational spectrum (using an accurate quartic force field), zero-point energy, and bonding of HNO using coupled-cluster ab initio methods. HNO is also very interesting because of the unique nature of its bonding characteristics. That is, the potential energy surface is very flat along the H-N bonding coordinate thereby giving unusual harmonic and fundamental vibrational frequencies, and the H-N bond energy is rather weak in comparison to other H-N bond energies. In fact, using experimental heats of formation for HNO, H, and NO, the H- bond energy is computed to be only 49.9 kcal/ mol (298 K). However, ab initio calculations of isodesmic reaction energies involving HNO, FNO, ClNO, and several other molecules have shown that there is an inconsistency in the experimental heats of formation of the XNO (X double bond H, F, and Cl) species. Hence the motivation for this study was to determine a very accurate (Delta)H(sub f, sup o) value for HNO using state-of-the-art ab initio methods. Based on many recent studies it is evident that the singles and doubles coupled-cluster method that includes a perturbational estimate of the effects of connected triple excitations, denoted CCSD(T), in conjunction with large one-particle basis sets should be reliable to better than +/- 0.8 kcal/mol for this quantity. The computational methodology is described in the next section followed by our results and discussion. Conclusions are presented in the final section.

Lee, Timothy J.↗
NASA NTRS1991

Heats of formation of bcc binary alloys

The method of Bozzolo, Ferrante and Smith is applied for the calculation of alloy energies for bcc elements. The heat of formation of several alloys is computed with the help of the Connolly-Williams method within the tetrahedron approximation. The dependence of the results on the choice of different sets of ordered structures is discussed.

Bozzolo, Guillermo↗
NASA NTRS1992

Heats of formation of bcc binary alloys

The method of Bozzolo, Ferrante and Smith is applied for the calculation of alloy energies for bcc elements. The heat of formation of several alloys is computed with the help of the Connolly-Williams method within the tetrahedron approximation. The dependence of the results on the choice of different sets of ordered structures is discussed.

Bozzolo, Guillermo↗
DOE OSTI2023

High-Accuracy Heats of Formation for Alkane Oxidation: From Small to Large via the Automated CBH-ANL Method

It is generally challenging to obtain high-accuracy predictions for the heat of formation for species with more than a handful of heavy atoms, such as those of importance in standard combustion mechanisms. To this end, we construct the CBH-ANL approach and illustrate that, for a set of 194 alkane oxidation species, it can be used to produce ΔH f (o K) values with 2σ uncertainties of 0.2-0.5 kcal mol -1 . This set includes the alkanes, hydroperoxides, and alkyl, peroxy, and hydroperoxyalkyl radicals for 17 representative hydrocarbon fuels containing up to 10 heavy atoms with various degrees of branching in the alkane backbone. The CBH-ANL approach, automated in the QTC and AutoMech software suites, builds balanced chemical equations for the calculation of ΔH f (o K), in which the reference species may be up to five heavy atoms. The high-level ANLo and ANL1 reference ΔH f (o K) values are further refined for even the largest of these reference species with a novel laddering approach. We perform a comprehensive quantification of the uncertainties for both the individual reference species (the largest of which is 0.15 kcal mol -1 ) and the propagation of those uncertainties when used in the calculation of ΔH f (o K) for the 194 target species. Here we examine the sensitivity of the predicted ΔH f (o K) values to (i) electronic energies from various methods, including ωB97X-D/cc-pVTZ, B2PLYP-D3/cc-pVTZ, CCSD(T)-F12b/cc-pVDZ-F12//B2PLYP-D3/cc-pVTZ, and CCSD(T)-F12b/cc-pVTZ-F12//B2PLYP-D3/cc-pVTZ; (ii) the zero-point vibrational energies (ZPVEs), where we consider harmonic ZPVEs as well as two scaling-based estimates of the anharmonic ZPVEs, all implemented for both ωB97X-D/cc-pVTZ and B2PLYP-D3/cc-pVTZ calculations; (iii) the particular CBH-ANL scheme employed; and (iv) the procedure for choosing the reference conformer for the analyses. The discussion concludes with a summary of the estimated overall uncertainty in the predictions and a validation of the predictions for the alkane subset.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1972

Photodissociation of OSCl2 in the vacuum ultraviolet - The heat of formation of SO.

The fluorescence spectra produced during the photodissociation were observed. Two excited states of SO were formed. The threshold energy of incident photons to produce one of the excited states was determined. The result is used to obtain the heat of formation of SO. No fluorescence due to molecular chlorine was observed, and the possible reasons for this are discussed.

Okabe, H.↗