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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 649 records · Page 36
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

DISCOVERY OF LOW DM FAST RADIO TRANSIENTS: GEMINGA PULSAR CAUGHT IN THE ACT

We report the discovery of several energetic radio bursts at 34 MHz, using the Gauribidanur radio telescope. The radio bursts exhibit two important properties associated with the propagation of astronomical signals through the interstellar medium: (i) frequency dependent dispersive delays across the observing bandwidth and (ii) Faraday rotation of the plane of linear polarization. These bursts sample a range of dispersion measures (DM; 1.4–3.6 pc cm{sup −3}) and show DM-variation at timescales of the order of a minute. Using groups of bursts having a consistent DM, we show that the bursts have originated from the radio-quiet gamma-ray pulsar Geminga. Detection of these bursts supports the existence of occasional radio emission from Geminga. The rare occurrence of these bursts, and the short timescale variation in their DM (if really caused by the intervening medium or the pulsar magnetosphere), might provide clues as to why the pulsar has not been detected in earlier sensitive searches. We present details of the observations and search procedure used to discover these bursts, a detailed analysis of their properties, and evidences of these bursts being associated with Geminga pulsar, and briefly discuss the possible emission mechanism of these bursts.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2012

CONDITIONS OF PASSAGE AND ENTRAPMENT OF TERRESTRIAL PLANETS IN SPIN-ORBIT RESONANCES

The dynamical evolution of terrestrial planets resembling Mercury in the vicinity of spin-orbit resonances is investigated using comprehensive harmonic expansions of the tidal torque taking into account the frequency-dependent quality factors and Love numbers. The torque equations are integrated numerically with a small step in time, including the oscillating triaxial torque components but neglecting the layered structure of the planet and assuming a zero obliquity. We find that a Mercury-like planet with a current value of orbital eccentricity (0.2056) is always captured in 3:2 resonance. The probability of capture in the higher 2:1 resonance is approximately 0.23. These results are confirmed by a semi-analytical estimation of capture probabilities as functions of eccentricity for both prograde and retrograde evolutions of spin rate. As follows from analysis of equilibrium torques, entrapment in 3:2 resonance is inevitable at eccentricities between 0.2 and 0.41. Considering the phase space parameters at the times of periastron, the range of spin rates and phase angles for which an immediate resonance passage is triggered is very narrow, and yet a planet like Mercury rarely fails to align itself into this state of unstable equilibrium before it traverses 2:1 resonance.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2014

Vibrational optical activity of chiral carbon nanoclusters treated by a generalized π-electron method

Cross sections of inelastic light scattering accompanied by vibronic excitation in large conjugated carbon structures is assessed at the π-electron level. Intensities of Raman and vibrational Raman optical activity (VROA) spectra of fullerenes are computed, relying on a single electron per atom. When considering only first neighbor terms in the Hamiltonian (a tight-binding (TB) type or Hückel-model), Raman intensities are captured remarkably well, based on comparison with frequency-dependent linear response of the self-consistent field (SCF) method. Resorting to π-electron levels when computing spectral intensities brings a beneficial reduction in computational cost as compared to linear response SCF. At difference with total intensities, the first neighbor TB model is found inadequate for giving the left and right circularly polarized components of the scattered light, especially when the molecular surface is highly curved. To step beyond first neighbor approximation, an effective π-electron Hamiltonian, including interaction of all sites is derived from the all-electron Fockian, in the spirit of the Bloch-equation. Chiroptical cross-sections computed by this novel π-electron method improve upon first-neighbor TB considerably, with no increase in computational cost. Computed VROA spectra of chiral fullerenes, such as C{sub 76} and C{sub 28}, are reported for the first time, both by conventional linear response SCF and effective π-electron models.

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

Control of optical response of a supported cluster on different dielectric substrates

We develop a computational method for optical response of a supported cluster on a dielectric substrate. The substrate is approximated by a dielectric continuum with a frequency-dependent dielectric function. The computational approach is based on our recently developed first-principles simulation method for photoinduced electron dynamics in real-time and real-space. The approach allows us to treat optical response of an adsorbate explicitly taking account of interactions at an interface between an adsorbate and a substrate. We calculate optical absorption spectra of supported Ag{sub n} (n = 2, 54) clusters, changing the dielectric function of a substrate. By analyzing electron dynamics in real-time and real-space, we clarify the mechanisms for variations in absorption spectra, such as peak shifts and intensity changes, relating to various experimental results for optical absorption of supported clusters. Attractive and repulsive interactions between an adsorbate and a substrate result in red and blue shifts, respectively, and the intensity decreases by energy dissipation into a substrate. We demonstrate that optical properties can be controlled by varying the dielectric function of a substrate.

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

Effect of Co{sub 2+} substitution in Mg{sub 0.5}Zn{sub 0.5−x}Co{sub x}Fe{sub 2}O{sub 4} ferrite nanoparticles: Study of structural, dielectric and magnetic properties

Polycrystalline samples of Mg{sub 0.5}Zn{sub 0.5−x}Co{sub x}Fe{sub 2}O{sub 4} (0 ≤ x ≤ 0.5) with x varying from 0.0-0.5 synthesized by sol-gel auto ignition method. The X-ray diffraction analysis with Retvield refinement reveals the formation of single phase cubic spinel structure. The frequency dependent of real part of dielectric constant has been measured at room temperature and at 100 °C by using an ac impedance analyzer. Except x = 0.5, an increase in the dielectric constant is observed with increase in Co{sup 2+} substitution. Magnetic response has been seen by vibrating sample magnetometer (VSM) at room temperature. The saturation magnetization (M{sub S}) and coercivity (H{sub C}) increase with increasing the Co{sub 2+} substitution. The cation distribution estimated by Mössbauer spectroscopy shows that Co{sub 2+} and Mg{sub 2+} ions have their preference towards octahedral B site, on the other hand Zn{sub 2+} ions preferentially occupy tetrahedral A site, whereas Fe{sub 3+} ions are randomly distributed over A- and B-site. The as obtained results indicated that the substitution of Co{sub 2+} has brought the significant changes in the structural, electrical and magnetic properties of as prepared Mg-Zn-Co multioxide nanocrystals.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Transport and dielectric properties of water and the influence of coarse-graining: Comparing BMW, SPC/E, and TIP3P models

Long-term molecular dynamics simulations are used to compare the single particle dipole reorientation time, the diffusion constant, the viscosity, and the frequency-dependent dielectric constant of the coarse-grained big multipole water (BMW) model to two common atomistic three-point water models, SPC/E and TIP3P. In particular, the agreement between the calculated viscosity of BMW and the experimental viscosity of water is satisfactory. We also discuss contradictory values for the static dielectric properties reported in the literature. Employing molecular hydrodynamics, we show that the viscosity can be computed from single particle dynamics, circumventing the slow convergence of the standard approaches. Furthermore, our data indicate that the Kivelson relation connecting single particle and collective reorientation time holds true for all systems investigated. Since simulations with coarse-grained force fields often employ extremely large time steps, we also investigate the influence of time step on dynamical properties. We observe a systematic acceleration of system dynamics when increasing the time step. Carefully monitoring energy/temperature conservation is found to be a sufficient criterion for the reliable calculation of dynamical properties. By contrast, recommended criteria based on the ratio of fluctuations of total vs. kinetic energy are not sensitive enough.

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

Ferromagnetic interactions and slow magnetic relaxation behaviors of two lanthanide coordination polymers bridged by 2,6-naphthalenedicarboxylate ligand

Two lanthanide-based frameworks: (Ln(phen)(NDA){sub 1.5}(H{sub 2}O)){sub n} (Ln=Gd(1), NDA=2,6-naphthalenedicarboxylate anion, phen=1,10-phenanthroline), and ([Dy(phen)(NDA){sub 1.5}]·0.5H{sub 2}NDA){sub n} (2) were structurally and magnetically characterized. Compound 1 exhibits 2D layer structure, belonging to the triclinic system with space group P−1, while compound 2 features a 3D framework with space group P−1. The magnetic studies revealed that ferromagnetic coupling existed between adjacent lanthanide ions in 1 and 2, and frequency-dependence out-of-phase signals in the measurement of alternate-current susceptibilities were observed for 2, albeit without reaching the characteristic maxima above 2 K, implying slow magnetic relaxation behavior in 2. After the application of a dc field, good peak shapes of ac signal were obtained and got the energy barrier ΔE/k{sub B}=29 K and the pre-exponential factor τ{sub 0}=4.47×10{sup −7} s at 2000 Oe field; and when the dc field was in 5000 Oe, giving ΔE/k{sub B}=40 K and τ{sub 0}=2.82×10{sup −6}. - Graphical abstract: Two novel lanthanide-based frameworks 1 and 2 were structurally and magnetically characterized. The results revealed that ferromagnetic coupling exists between adjacent lanthanide ions in 1 and 2, and 2 displayed slow magnetic relaxation behavior with the energy barrier of 29 K. - Highlights: • Two lanthanide frameworks were synthesized and magnetically characterized. • The magnetism studies indicate slow magnetic relaxation behavior in 2. • Weak ferromagnetic coupling existing between adjacent lanthanide centers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

ON THE EFFECTS OF OPTICALLY THICK GAS (DISKS) AROUND MASSIVE STARS

Numerical simulations have shown that the often cited radiation pressure barrier to accretion onto massive stars can be circumvented, when the radiation field is highly anisotropic in the presence of a circumstellar accretion disk with high optical depth. Here, these studies of the so-called flashlight effect are expanded by including the opacity of the innermost dust-free but potentially optically thick gas regions around forming massive stars. In addition to frequency-dependent opacities for the dust grains, we use temperature- and density-dependent Planck and Rosseland mean opacities for the gas. The simulations show that the innermost dust-free parts of the accretion disks are optically thick to the stellar radiation over a substantial fraction of the solid angle above and below the disk's midplane. The temperature in the shielded disk region decreases faster with radius than in a comparison simulation with a lower constant gas opacity, and the dust sublimation front is shifted to smaller radii. The shielding by the dust-free gas in the inner disk thus contributes to an enhanced flashlight effect, which ultimately results in a smaller opening angle of the radiation pressure driven outflow and in a much longer timescale of sustained feeding of the circumstellar disk by the molecular cloud core. We conclude that it is necessary to properly account for the opacity of the inner dust-free disk regions around forming massive stars in order to correctly assess the effectiveness of the flashlight effect, the opening angle of radiation pressure driven outflows, and the lifetime and morphological evolution of the accretion disk.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2014

Growth and characterization of undoped and Mn doped lead-free piezoelectric NBT–KBT single crystals

Highlights: • Single crystals of undoped and Mn doped NKBT crystals are grown by spontaneous nucleation. • Temperature and frequency dependent dielectric constant and loss are measured. • Dielectric constant has increased and the loss has reduced on Mn doped NKBT. • Concentration of oxygen vacancies has been reduced in Mn doped NKBT. • The activation energy for undoped and Mn doped NKBT are calculated. - Abstract: Lead-free piezoelectric single crystals of undoped and 1 wt% Mn doped 0.80 Na{sub 0.5}Bi{sub 0.5}TiO{sub 3}–0.20 K{sub 0.5}Bi{sub 0.5}TiO{sub 3} (NKBT) was grown using self-flux. Powder X-ray diffraction analysis revealed that the grown crystals belong to tetragonal system at room temperature. The lattice strain was calculated from Williamson Hall relation for undoped and Mn doped NKBT crystals. A significant change is observed in dielectric behavior of Mn doped NKBT when compared to undoped sample. The diffuseness increased substantially on Mn doped NKBT which masked the ferroelectric to antiferroelectric transition in the dielectric constant plot. The AC impedance study revealed that the conduction is governed by the singly ionized oxygen vacancy. Further, the decrease in the conductivity on Mn doping suggests that Mn replaces the Bi vacancy, which reduces the oxygen vacancy.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Static and dynamic polarizability for C{sup 2+} in Rydberg states

This work presents results from a non-perturbative calculation of dynamic polarizability of C III ions in 1s{sup 2}2sns ({sup 1}S{sup e}) Rydberg states. We employ a two-state model for dressed atomic states to investigate the effect of the frequency-dependent polarizability of optically dressed 1s{sup 2}2sns({sup 1}S{sup e}) states (n = 5 − 12) on transitions to nearby states (1s{sup 2}2pns({sup 1}P{sub 1}{sup o})). Our model calculation results indicate that the resonance structure of the polarizabilities is entirely captured by the transition terms whereas the free electron polarizability only provides a smooth background. The resonance structure is evident in the plots and the widths increase with increasing principal quantum number. This work refers to highly excited 1s{sup 2}2sns ({sup 1}S) Rydberg states, embedded in the electric dipole field of the 2s – 2p core transition in Li-like C{sup 3+} ion. The contributions of the individual transitions to the static polarizabilities of these Rydberg states are obtained from the use of the sum-over-state method. To this aim, both the C{sup 2+} ground state and the C{sup 3+} target state energies have been carefully calculated based on the configuration interactions method implemented in the General-purpose Relativistic Atomic Structure Package. Agreement is reasonably good with existing data wherever available. These results are believed to be the first such values for this system and will be important for ionic spectroscopy and plasma diagnostics.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2015

BROADBAND RADIO POLARIMETRY AND FARADAY ROTATION OF 563 EXTRAGALACTIC RADIO SOURCES

We present a broadband spectropolarimetric survey of 563 discrete, mostly unresolved radio sources between 1.3 and 2.0 GHz using data taken with the Australia Telescope Compact Array. We have used rotation-measure synthesis to identify Faraday-complex polarized sources, those objects whose frequency-dependent polarization behavior indicates the presence of material possessing complicated magnetoionic structure along the line of sight (LOS). For sources classified as Faraday-complex, we have analyzed a number of their radio and multiwavelength properties to determine whether they differ from Faraday-simple polarized sources (sources for which LOS magnetoionic structures are comparatively simple) in these properties. We use this information to constrain the physical nature of the magnetoionic structures responsible for generating the observed complexity. We detect Faraday complexity in 12% of polarized sources at ∼1′ resolution, but we demonstrate that underlying signal-to-noise limitations mean the true percentage is likely to be significantly higher in the polarized radio source population. We find that the properties of Faraday-complex objects are diverse, but that complexity is most often associated with depolarization of extended radio sources possessing a relatively steep total intensity spectrum. We find an association between Faraday complexity and LOS structure in the Galactic interstellar medium (ISM) and claim that a significant proportion of the Faraday complexity we observe may be generated at interfaces of the ISM associated with ionization fronts near neutral hydrogen structures. Galaxy cluster environments and internally generated Faraday complexity provide possible alternative explanations in some cases.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2012

Wireless Transmission of Monitoring Data out of the HADES Underground Laboratory - 12450

As part of the European 7. framework project MoDeRn, Nuclear Research and Consultancy Group (NRG) performed experiments in order to demonstrate the feasibility of wireless data transmission through the subsurface over larger distances by low frequency magnetic fields. The main objective of NRG's contribution is to characterize and optimize the energy use of this technique within the specific context of post-closure monitoring. For this, measurements have been performed in the HADES underground laboratory located at Mol, Belgium, at 225 m depth. The experimental set-up makes use of a loop antenna for the transmitter that has been matched into the existing infrastructure of the HADES. The experimental work of NRG is divided into several stages: in 2010, the necessary hardware has been designed and assembled and tested in the Netherlands. Site-specific magnetic background noise in Mol and frequency-dependent signal attenuation by the geologic medium has been measured. Signal transmission has been demonstrated and several transmission channels around 1 kHz have been identified. In 2011, additional measures and experiments have been performed in order to characterize and test relevant element of the transmission chain and to optimize the energy use of the set-up. A mathematical model description has been developed that includes the most relevant characteristics of the transmitter, receiver and transmission path and was used to analyse possible options to optimize the set-up. In 2012, experiments are planned in order to test several data transmission options. Results so far have shown that signal transmission over larger distances through the subsurface is feasible. However, to make quantitative conclusions on the energy need per bit of transmitted data, additional experiments planned in 2012 are necessary. The experimental and theoretical results gained by NRG, as part of the European 7. framework project MoDeRn, so far demonstrated that signal transmission through 225 m of a geological medium is feasible, even in case of a 'good conductor' as present in Mol. At this particular site the transmission distance through the different layers of clay and sandy aquifers is larger than the skin depth and clearly extends the near-field. The step from signal to data transmission will be made in 2012 and is essential to be able to make quantitative statements of the energy use per transmitted data bit. (authors)

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2016

LOW-FREQUENCY OBSERVATIONS OF LINEARLY POLARIZED STRUCTURES IN THE INTERSTELLAR MEDIUM NEAR THE SOUTH GALACTIC POLE

We present deep polarimetric observations at 154 MHz with the Murchison Widefield Array (MWA), covering 625 deg{sup 2} centered on α = 0{sup h}and δ = −27°. The sensitivity available in our deep observations allows an in-band, frequency-dependent analysis of polarized structure for the first time at long wavelengths. Our analysis suggests that the polarized structures are dominated by intrinsic emission but may also have a foreground Faraday screen component. At these wavelengths, the compactness of the MWA baseline distribution provides excellent snapshot sensitivity to large-scale structure. The observations are sensitive to diffuse polarized emission at ∼54′ resolution with a sensitivity of 5.9 mJy beam{sup −1} and compact polarized sources at ∼2.′4 resolution with a sensitivity of 2.3 mJy beam{sup −1} for a subset (400 deg{sup 2}) of this field. The sensitivity allows the effect of ionospheric Faraday rotation to be spatially and temporally measured directly from the diffuse polarized background. Our observations reveal large-scale structures (∼1°–8° in extent) in linear polarization clearly detectable in ∼2 minute snapshots, which would remain undetectable by interferometers with minimum baseline lengths of >110 m at 154 MHz. The brightness temperature of these structures is on average 4 K in polarized intensity, peaking at 11 K. Rotation measure synthesis reveals that the structures have Faraday depths ranging from −2 to 10 rad m{sup −2} with a large fraction peaking at approximately +1 rad m{sup −2}. We estimate a distance of 51 ± 20 pc to the polarized emission based on measurements of the in-field pulsar J2330–2005. We detect four extragalactic linearly polarized point sources within the field in our compact source survey. Based on the known polarized source population at 1.4 GHz and non-detections at 154 MHz, we estimate an upper limit on the depolarization ratio of 0.08 from 1.4 GHz to 154 MHz.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2015

Self-consistent Kohn-Sham method based on the adiabatic-connection fluctuation-dissipation theorem and the exact-exchange kernel

A self-consistent Kohn-Sham method based on the adiabatic-connection fluctuation-dissipation (ACFD) theorem, employing the frequency-dependent exact exchange kernel f{sub x} is presented. The resulting SC-exact-exchange-only (EXX)-ACFD method leads to even more accurate correlation potentials than those obtained within the direct random phase approximation (dRPA). In contrast to dRPA methods, not only the Coulomb kernel but also the exact exchange kernel f{sub x} is taken into account in the EXX-ACFD correlation which results in a method that, unlike dRPA methods, is free of self-correlations, i.e., a method that treats exactly all one-electron systems, like, e.g., the hydrogen atom. The self-consistent evaluation of EXX-ACFD total energies improves the accuracy compared to EXX-ACFD total energies evaluated non-self-consistently with EXX or dRPA orbitals and eigenvalues. Reaction energies of a set of small molecules, for which highly accurate experimental reference data are available, are calculated and compared to quantum chemistry methods like Møller-Plesset perturbation theory of second order (MP2) or coupled cluster methods [CCSD, coupled cluster singles, doubles, and perturbative triples (CCSD(T))]. Moreover, we compare our methods to other ACFD variants like dRPA combined with perturbative corrections such as the second order screened exchange corrections or a renormalized singles correction. Similarly, the performance of our EXX-ACFD methods is investigated for the non-covalently bonded dimers of the S22 reference set and for potential energy curves of noble gas, water, and benzene dimers. The computational effort of the SC-EXX-ACFD method exhibits the same scaling of N{sup 5} with respect to the system size N as the non-self-consistent evaluation of only the EXX-ACFD correlation energy; however, the prefactor increases significantly. Reaction energies from the SC-EXX-ACFD method deviate quite little from EXX-ACFD energies obtained non-self-consistently with dRPA orbitals and eigenvalues, and the deviation reduces even further if the Coulomb kernel is scaled by a factor of 0.75 in the dRPA to reduce self-correlations in the dRPA correlation potential. For larger systems, such a non-self-consistent EXX-ACFD method is a competitive alternative to high-level wave-function-based methods, yielding higher accuracy than MP2 and CCSD methods while exhibiting a better scaling of the computational effort than CCSD or CCSD(T) methods. Moreover, EXX-ACFD methods were shown to be applicable in situation characterized by static correlation.

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

Electrical properties of dispersions of graphene in mineral oil

Dispersions of graphene in mineral oil have been prepared and electrical conductivity and permittivity have been measured. The direct current (DC) conductivity of the dispersions depends on the surface characteristics of the graphene platelets and followed a percolation model with a percolation threshold ranging from 0.05 to 0.1 wt. %. The difference in DC conductivities can be attributed to different states of aggregation of the graphene platelets and to the inter-particle electron transfer, which is affected by the surface radicals. The frequency-dependent conductivity (σ(ω)) and permittivity (ε(ω)) were also measured. The conductivity of dispersions with particle contents much greater than the percolation threshold remains constant and equal to the DC conductivity at low frequencies ω with and followed a power-law σ(ω)∝ ω{sup s} dependence at very high frequencies with s≈0.9. For dispersions with graphene concentration near the percolation threshold, a third regime was displayed at intermediate frequencies indicative of interfacial polarization consistent with Maxwell-Wagner effect typically observed in mixtures of two (or more) phases with very distinct electrical and dielectric properties.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Magnetic field, frequency and temperature dependence of complex conductance of ultrathin La1.65Sr0.45CuO4/La2CuO4 films and the organic superconductors κ-(BEDT-TTF)2Cu[N(CN)2]Br

We used atomic-layer molecular beam epitaxy (ALL-MBE) to synthesize bilayer films of a cuprate metal (La1.65Sr0.45CuO4La1.65Sr0.45CuO4, LSCO) and a cuprate insulator (La2CuO4La2CuO4, LCO), in which interface superconductivity occurs in a layer that is just one-half unit cell thick. We have studied the magnetic field and temperature dependence of the complex sheet conductance, σ(ω)σ(ω), of these films, and compared them to κκ-(BEDT-TTF)2Cu[N(CN)2]Br2Cu[N(CN)2]Br single crystals. The magnetic field HH was applied both parallel and perpendicular to the 2D conducting layers. Experiments have been carried out at frequencies between 23 kHz and 50 MHz using either two-coil mutual inductance technique, or the LC resonators with spiral or rectangular coils. The real and the imaginary parts of the mutual-inductance M(T,ω)M(T,ω) between the coil and the sample were measured and converted to complex conductivity. For HH perpendicular to the conducting layers, we observed almost identical behavior in both films and κκ-Br single crystals: (i) the transition onset in the inductive response, L-1kLk-1(T) occurs at a temperature lower by 2 K than in Reσ(T)Reσ(T), (ii) this shift is almost constant with magnetic field up to 8 T; (iii) the vortex diffusion constant D(T)D(T) is exponential due to pinning of vortex cores. These results can be described by the extended dynamic theory of the Berezinski–Kosterlitz–Thouless (BKT) transition and dynamics of bound vortex–antivortex pairs with short separation lengths.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2017

Accuracy of finite-difference harmonic frequencies in density functional theory

Analytic Hessians are often viewed as essential for the calculation of accurate harmonic frequencies, but the implementation of analytic second derivatives is nontrivial and solution of the requisite coupled-perturbed equations engenders a sizable memory footprint for large systems, given that these equations are not required for energy and gradient calculations in density functional theory. Here, we benchmark the alternative approach to harmonic frequencies based on finite differences of analytic first derivatives, a procedure that is amenable to large-scale parallelization. Not only for absolute frequencies but also for isotopic and conformer-dependent frequency shifts in flexible molecules, we find that the finite-difference approach exhibits mean errors < 0.1 cm -1 as compared to results based on an analytic Hessian. For very small frequencies corresponding to nonbonded vibrations in noncovalent complexes (for which the harmonic approximation is questionable anyway), the finite-difference error can be larger, but even in these cases the errors can be reduced below 0.1 cm -1 by judicious choice of the displacement step size and a higher-order finite-difference approach. Finally, the surprising accuracy and robustness of the finite-difference results suggests that availability of the analytic Hessian is not so important in today's era of commodity processors that are readily available in large numbers.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2023

Systematically derived thermodynamic properties for alkane oxidation

Key combustion properties, such as ignition delay time, show strong sensitivity to the thermochemistry of the main species in the standard radical oxidation pathway at low temperatures (600-1000K). Significant uncertainties persist in current estimates of thermodynamic properties, particularly for the larger species of relevance to common practical fuels. In this article, we use advanced computational schemes to evaluate thermodynamic properties for the fuel, fuel radical, peroxy, hydroperoxy-alkyl radical, and hydroperoxide species for a set of 17 fuels containing up to 9 carbon atoms, and with various degrees of branching in the alkane backbone. The procedure, termed STAR-1D, combines conformer sampling to find the minimum geometry, B2PLYP-D3/cc-pVTZ harmonic frequency evaluations, and omega B97X-D/cc-pVTZ one-dimensional torsional mapping. It includes two physically-based scaling routines: a frequency-dependent scaling to B2PLYP-D3/cc-pVTZ anharmonic frequencies and a scaling of one-dimensional omega B97X-D/ccpVTZ torsional profiles to reproduce the product of the B2PLYP-D3/cc-pVTZ frequencies in the harmonic limit. Substantive comparisons with existing experimental databases, together with careful examinations of key theoretical assumptions, are used to explore the accuracy of the predictions. These computationally intensive explorations of 195 species were facilitated by automated thermochemistry software. Further, high accuracy 0 K heats of formation from a separate study are used with the STAR-1D computations to generate NASA polynomial representations. In addition to their intrinsic value, the present results also provide a reliable database for the optimization of group additivity or machine learning schemes for scaling to larger combustion systems. Towards this end a complementary extensive conformational analysis is carried out for the medium sized species and the thermodynamic properties of the lowest energy hydrogen-bonded and non-hydrogen bonded conformers are contrasted for larger hydroperoxy-alkyl radical species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗