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At least 1,045 records · Page 58
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Understanding polaronic transport in complex oxides by combining precise synthesis and first-principles many-body theory

In complex oxides, charge carriers often couple strongly with lattice vibrations to form polarons–entangled electron–phonon quasiparticles whose transport properties remain difficult to characterize. Experimental access to intrinsic polaronic transport requires ultraclean samples, while theoretical description demands methods beyond low-order perturbation theory. Here, we show a predictive theory–experiment workflow to study polaron transport in complex oxides. Focusing on a prototypical polaronic oxide, anatase TiO 2 , we combine growth of high-quality oxygen-vacancy-doped films using hybrid molecular beam epitaxy with a first-principles electron–phonon diagrammatic Monte-Carlo (FEP-DMC) framework recently developed for accurate polaron predictions. Our films exhibit record-high electron mobility for anatase TiO 2 , in excellent agreement with FEP-DMC calculations conducted prior to experiment, which predict a room-temperature mobility of 45 ± 15 cm −2 V −1 s −1 and a mobility-temperature scaling of μ ∝ T −1.9 ± 0.077 . Microscopic analysis using scanning transmission electron microscopy and x-ray photoelectron spectroscopy reveals the role of oxygen vacancies in modulating transport at lower temperatures. FEP-DMC further provides quantitative insight into polaron formation energy, phonon cloud distribution, lattice distortion around the polaron, and the polaronic contribution to mobility. Together, these results provide a deeper microscopic understanding of large-polaron transport in a complex oxide and provide the blueprint to characterize other polaronic materials.

anatase TiO2↗
NASA NTRS1987

(2 + 1) resonant enhanced multiphoton ionization of H2 via the E,F 1Sigma(+)g state

In this paper, the results of ab initio calculations of photoelectron angular distributions and vibrational branching ratios for the (2 + 1) resonant enhanced multiphoton ionization (REMPI) of H2 via the E,F 1Sigma(+)g state are reported, and these are compared with the experimental data of Anderson et al. (1984). These results show that the observed non-Franck-Condon behavior is predominantly due to the R dependence of the transition matrix elements, and to a lesser degree to the energy dependence. This work presents the first molecular REMPI study employing a correlated wave function to describe the Rydberg-valence mixing in the resonant intermediate state.

Rudolph, H.↗
NASA NTRS1989

Fast molecular shocks. II - Emission from fast dissociative shocks

The line radiations emitted in the cooling gas behind a fast dissociative shock are studied. The intensities emitted in high rotational transitions of the neutral molecules CO, SiO, HCN, CN, NO, and SO are estimated, as well as in rovibrational transitions of the molecular ions HeH(+) and OH(+) in radio recombination lines of atomic hydrogen and in fine-structure transitions of C, C(+), O, and Si(+). The predictions are compared with the observed intensities of line emission from the Orion-KL region. For Orion-KL the observations do not exclude, but probably do not require, the presence of a fast dissociative shock. Emission from SiO in high-J rotational states and from vibrationally excited OH(+), HeH(+), HeH(+), and SO(+) may be detectable from dissociative shocks under suitable conditions of preshock density and shock velocity; such emission may prove to be a useful diagnostic probe of fast shock activity.

Neufeld, David A.↗
NASA NTRS2011

A Quantitative, Time-Dependent Model of Oxygen Isotopes in the Solar Nebula: Step one

The remarkable discovery that oxygen isotopes in primitive meteorites were fractionated along a line of slope I rather than along the typical slope 0,52 terrestrial fractionation line occurred almost 40 years ago, However, a satisfactory, quantitative explanation for this observation has yet to be found, though many different explanations have been proposed, The first of these explanations proposed that the observed line represented the final product produced by mixing molecular cloud dust with a nucleosynthetic component, rich in O-16, possibly resulting from a nearby supernova explosion, Donald Clayton suggested that Galactic Chemical Evolution would gradually change the oxygen isotopic composition of the interstellar grain population by steadily producing O-16 in supernovae, then producing the heavier isotopes as secondary products in lower mass stars, Thiemens and collaborators proposed a chemical mechanism that relied on the availability of additional active rotational and vibrational states in otherwise-symmetric molecules, such as CO2, O3 or SiO2, containing two different oxygen isotopes and a second, photochemical process that suggested that differential photochemical dissociation processes could fractionate oxygen , This second line of research has been pursued by several groups, though none of the current models is quantitative,

Nuth, J. A.↗
DOE OSTI2022

Exciton-vibrational dynamics induces efficient self-trapping in a substituted nanoring

Cycloparaphenylenes, being the smallest segments of carbon nanotubes, have emerged as prototypes of the simplest carbon nanohoops. Their unique structure–dynamics–optical properties relationships have motivated a wide variety of synthesis of new related nanohoop species. Studies of how chemical changes, introduced in these new materials, lead to systems with new structural, dynamics and optical properties, expand their functionalities for optoelectronics applications. Herein, we study the effect that conjugation extension of a cycloparaphenylene through the introduction of a satellite tetraphenyl substitution has on its structural and dynamical properties. Our non-adiabatic excited state molecular dynamics simulations suggest that this substitution accelerates the electronic relaxation from the high-energy band to the lowest excited state. This is partially due to efficient conjugation achieved between specific phenyl units as introduced by the tetraphenyl substitution. We observe a particular exciton redistribution during relaxation, in which the tetraphenyl substitution plays a significant role. As a result, an efficient inter-band energy transfer takes place. Besides, the observed phonon-exciton interplay induces a significant exciton self-trapping. Finally, our results encourage and guide the future studies of new phenyl substitutions in carbon nanorings with desired optoelectronic properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1992

Radiative energy transfer in molecular gases

Basic formulations, analyses, and numerical procedures are presented to study radiative interactions in gray as well as nongray gases under different physical and flow conditions. After preliminary fluid-dynamical considerations, essential governing equations for radiative transport are presented that are applicable under local and nonlocal thermodynamic equilibrium conditions. Auxiliary relations for relaxation times and spectral absorption models are also provided. For specific applications, several simple gaseous systems are analyzed. The first system considered consists of a gas bounded by two parallel plates having the same temperature. Within the gas there is a uniform heat source per unit volume. For this system, both vibrational nonequilibrium effects and radiation conduction interactions are studied. The second system consists of fully developed laminar flow and heat transfer in a parallel plate duct under the boundary condition of a uniform surface heat flux. For this system, effects of gray surface emittance are studied. With the single exception of a circular geometry, the third system is considered identical to the second system. Here, the influence of nongray walls is also studied.

Tiwari, Surendra N.↗
DOE OSTI2024

Anion photoelectron spectroscopy and chemical bonding of ThS 2 – and ThSO –

Anion photoelectron spectra of ThSO – and ThS 2 – were recorded using the third (355 nm) harmonic of an Nd-YAG laser; these provided the measured vertical detachment energies of each anion. The experiments are supported by extensive coupled cluster calculations on ThSO, ThSO – , ThS 2 , and ThS 2 – , as well as the oxygen congeners ThO 2 and ThO 2 – . The ab initio calculations, which included complete basis set extrapolations, spin–orbit effects using four-component coupled cluster, and higher-order correlation contributions through CCSDT(Q), yielded an adiabatic electron affinity for ThO 2 – that was within 0.02 eV of the previously determined experimental value. The singly occupied molecular orbital (SOMO) in all three anions corresponds primarily to the 7s orbital on Th. Successive substitution of S for each O in ThO 2 leads to larger electron affinities and smaller bond angles in the neutral molecules, but larger angles in the anions. As demonstrated by Franck–Condon simulations of the spectra using the CCSD(T) spectroscopic constants, substitution of O by S significantly complicates the resulting detachment spectra due to the lower vibrational frequencies in the sulfur species. Altogether the calculated vertical detachment energies are in very good agreement with the experiment. In addition to the adiabatic electron affinities of each species, atomization energies and heats of formation have also been determined via the FPD approach with expected uncertainties of 1–2 kcal/mol.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1971

Deactivation of N2 A/super 3/Sigma/sub u/+ molecules in the aurora.

Recent rocket observations of the molecular nitrogen Vegard-Kaplan system in the aurora have been reinterpreted using an atmospheric model based on mass spectrometer measurements in an aurora of similar intensity at the same time of year. It is found that the population rates of the considered levels in the aurora are accurately determined by radiative cascade from two other states excited by direct electron impact. In some bright auroras the role of NO in quenching the lower vibrational levels of the A state is significant. The conclusions are based on a number of relevant auroral observations in combination with calculations using electron cross section and transition probability measurements by Shemansky and Broadfoot (1971).

Shemansky, D. E.↗
NASA NTRSDate not supplied

Analysis of Nonequilibrium Molecular Nitrogen Ultraviolet Radiation in Pure N2 Shockwaves

This paper presents an analysis of data previously reported from a test series in the Electric Arc Shock Tube Facility for incident shocks composed of pure Nitrogen. The present work focuses on the lowest velocity measured in the test (approximately 7 km/s) where molecular radiation is significant. Analysis of the spectral data with the NEQAIR radiative transport code obtains post-shock trends in temperature and number densities of the states of N2. The results suggest that chemical, and possibly thermal, equilibrium has not been obtained within the distance/time measured (about 5 cm/120 s). In the nonequilibrium region of the shock, differences between rotational temperatures of different species are observed, as well as differences between rotational and vibrational temperatures. Population of rotational states above the dissociation limit is observed to occur over a distance of several cm. Finally, these data suggest that predissociation strongly affects the C^3 Π_u state of N2, leading to a lower measured radiation than predicted. An effective average pre-dissociation rate is shown to produce reasonable agreement under quasi-steady state approximation.

Augustin Tibere Inglesse↗
NASA NTRSDate not supplied

Analysis of nonequilibrium molecular nitrogen ultraviolet radiation in pure N2 shockwaves

An analysis of data previously reported from a test series in the Electric Arc Shock Tube Facility for incident shocks composed of pure Nitrogen was performed. The present work focuses on the lowest velocity measured in the test (approximately 7 km/s) where molecular radiation is significant. Analysis of the spectral data with the NEQAIR radiative transport code obtains post-shock trends in temperature and number densities of the states of N2. The results suggest that chemical, and possibly thermal, equilibrium has not been obtained within the distance/time measured (about 5 cm/120 ms). In the nonequilibrium region of the shock, differences between rotational temperatures of different species are observed, as well as differences between rotational and vibrational temperatures. Population of rotational states above the dissociation limit is observed to occur over a distance of several cm. Finally, these data suggest that predissociation strongly affects the C^3 Π_u state of N2, leading to a lower measured radiation than predicted. An effective average pre-dissociation rate is shown to produce reasonable agreement under quasi-steady state approximation.

Augustin Tibere-Inglesse↗
DOE OSTI2020

Excited state dynamics of cis , cis -1,3-cyclooctadiene: UV pump VUV probe time-resolved photoelectron spectroscopy

We present UV pump, vacuum ultraviolet probe time-resolved photoelectron spectroscopy measurements of the excited state dynamics of cis,cis-1,3-cyclooctadiene. A 4.75 eV deep UV pump pulse launches a vibrational wave packet on the first electronically excited state, and the ensuing dynamics are probed via ionization using a 7.92 eV probe pulse. The experimental results indicate that the wave packet undergoes rapid internal conversion to the ground state in under 100 fs. Comparing the measurements with electronic structure and trajectory surface hopping calculations, we are able to interpret the features in the measured photoelectron spectra in terms of ionization to several states of the molecular cation.

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

Mechanisms and dynamics of the NH + 2 + H + and NH + + H + + H fragmentation channels upon single-photon double ionization of NH 3

We present state-selective measurements on the NH$_2^{+}$ + H$^{+}$ and NH$^{+}$ + H$^{+}$ + H dissociation channels following single-photon double ionization at 61.5 eV of neutral NH$_{3}$, where the two photoelectrons and two cations are measured in coincidence using 3-D momentum imaging. Three dication electronic states are identified to contribute to the NH$_2^{+}$ + H$^{+}$ dissociation channel, where the excitation in one of the three states undergoes intersystem crossing prior to dissociation, producing a cold NH$_2^+$ fragment. In contrast, the other two states directly dissociate, producing a ro-vibrationally excited NH$_2^+$ fragment with roughly 1 eV of internal energy. The NH$^{+}$ + H$^{+}$ + H channel is fed by direct dissociation from three intermediate dication states, one of which is shared with the NH$_2^{+}$ + H$^{+}$ channel. We find evidence of autoionization contributing to each of the double ionization channels. Finally, the distributions of the relative emission angle between the two photoelectrons, as well as the relative angle between the recoil axis of the molecular breakup and the polarization vector of the ionizing field, are also presented to provide insight on the ionization mechanisms for the different dication states.

74 ATOMIC AND MOLECULAR PHYSICS↗
NASA NTRS1984

Interstellar Grain Mantles

Techniques for determining the composition of small dust grains in interstellar matter are discussed. The best way to study the composition of interstellar grain mantles is by infrared spectroscopy. The absorption features in a complete infrared spectrum from 2 to 15 microns can be used as fingerprints to identify the absorbing molecule. Ground-based observations around 3 microns confirmed the presence of H2O ice in interstellar grain mantles, through the detection of the 3.08 micron OH stretching vibration. The detection of other molecules, in particular the carbon bearing molecules, is however hampered by atmospheric absorption in the 5-8 micron region and the presence of the strong ice and silicate bands, which dominate the 3 and 10 micron region respectively. Kuiper Airborne Observatory observations of the 5-8 micron region of the spectrum are therefore extremely important to determine the composition of interstellar grain mantles. The 5 to 8 micron spectra of molecular cloud sources was obtained using a 24 detector grating spectrometer. An important characteristic of this spectrometer is that the whole spectrum is obtained simultaneously. It is therefore relatively easy to correct for atmospheric transmission.

Witteborn, F.↗
DOE OSTI2025

Abnormal Slow Phonon Dynamics Toward Prolonging Excited States Dynamics Enabled by Crystalline‐Assembling Donor–Acceptor Molecules

Phonon dynamics are a critical factor to control the optical properties of excited states in light-emitting materials. Here, we report an extremely slow relaxation of photoexcited lattice vibrations enabled by assembling the donor-acceptor (D–A) molecules [2-(9,9-dimethylacridin-10(9H)-yl)-9,9-dimethyl-9H-thioxanthene 10,10-dioxide], namely AC molecules, into dipolar crystal. By using photoexcitation-modulated Raman spectroscopy, we find that the crystalline-lattice vibrations monitored by Raman-scattering laser beam of 785 nm demonstrate an un-usual slow relaxation in the time scale of seconds after ceasing photoexcitation beam of 343 nm in such dipolar crystal. This presents extremely slow phonon dynamics enabled by crystalline-assembling the D–A molecules into a dipolar crystal. Simultaneously, the photoluminescence (PL) exhibits a prolonged behavior, lasting 10 ms after ceasing photoexcitation in dipolar AC crystal. This phenomenon provides an experimental hypothesis that the slow phonon dynamics function as an important mechanism to unusually prolong excited states dynamics upon crystalline-assembling the D–A molecules into dipolar crystal. Here, this hypothesis can be verified by directly suppressing the phonon dynamics through freezing D–A molecular liquid into dipolar crystalline solid at 77 K to largely prolong the PL to 1 s- after removing photoexcitation. Clearly, crystalline-assembling D–A molecules provide the necessary conditions to enable slow phonon dynamics toward prolonging excited states dynamics.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Vibrational Dynamics and Phase Transitions of Hydrazine to 50 GPa

The high pressure behavior of hydrazine, N 2 H 4 , has been investigated to 50 GPa at room temperature using infrared and Raman spectroscopy to explore pressure induced phase transitions and changes in hydrogen bonding. Three solid–solid phase transitions were detected at 11, 21, and 32 GPa on room temperature compression through dramatic changes in the lattice vibration and N–H stretching regions with increasing pressure in both measurement techniques. The transition to phase IV, which appears at 32 GPa, exhibits increased hydrogen bonding with significant hysteresis, persisting to 9 GPa on decompression. This work presents a detailed analysis of the pressure dependence of mode shifts and calculations of mode Grüneisen parameters as well as a determination of an approximate thermodynamic Grüneisen parameter. We compare these results to the behavior of other small molecular materials such as ammonia and water and explore the evolution of hydrogen bonding in hydrazine toward the symmetrically hydrogen bonded state, which has previously been suggested by theoretical computations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Critical Role of Framework Flexibility and Disorder in Driving High Ionic Conductivity in LiNbOCl 4

Understanding Li-ion transport is key for the rational design of superionic solid electrolytes with exceptional ionic conductivities. LiNbOCl 4 is reported to be one of the most highly conducting materials in the recently realized new class of soft oxyhalide solid electrolytes, exhibiting an ionic conductivity of ~11 mS·cm -1 . Here, we apply X-ray/neutron diffraction and pair distribution function analysis - coupled with density functional theory/ab-initio molecular dynamics - to determine a structural model that provides a rationale for the high conductivity that we observe experimentally in this nanocrystalline solid. We show that it arises from unusually high framework flexibility at room temperature. This owes to isolated 1-D [NbOCl 4 ] - anionic chains which exhibit energetically favorable orientational disorder that is - in turn - correlated to multiple, disordered and equi-energetic Li + sites in the lattice. As the Li-ions sample the 3-D energy landscape with a fast predicted diffusion coefficient of 5.1 x 10 -7 cm 2 /s at room temperature (σ i calc = 17.4 mS·cm -1 ), the inorganic polymer chains can reorient or vice versa. The activation energy barrier for Li migration through the frustrated energy landscape is especially reduced by the elastic nature of the NbO 2 Cl 4 octahedra evident from very widely dispersed Cl-Nb-Cl bond angles in AIMD snapshots at 300 K. The phonon spectra are predominantly influenced by Cl vibrations in the low energy range, and there is strong overlap between the framework (Cl, Nb) and Li partial pDOS in the region between 1.2 - 4.0 THz. The framework flexibility is also reflected in a relatively low bulk modulus of 22 GPa. In conclusion, our findings pave the way for investigation of future “flex-ion” inorganic solids and open up a new direction for the design of high conductivity, soft solid electrolytes for all-solid-state batteries.

AIMD↗
NASA NTRS1979

Electron impact study of potassium hydroxide

An attempt is made to measure the sum of the elastic, rotational and vibrational scattering of electrons by KOH at low impact energies (5 to 20 eV) at angles from 10 to 120 deg. Energy loss spectra taken in the 0 to 18 eV range using an electron impact spectrometer are used to identify the species contributing to electric scattering. At temperatures between 300 and 500 C, only inelastic spectral features belonging to water are detected, while at temperatures from 500 to 800 C strong atomic K lines, indicative of molecular dissociation, and H2 energy loss features become prominent. No features attributable to KOH, the KOH dimer, O2 or potassium oxides were observed, due to the effects of the dissociation products, and it is concluded that another technique will have to be developed in order to measure electron scattering by KOH.

Vuskovic, L.↗
NASA NTRS1989

A new analysis of the vibration-rotation spectrum of CH from solar spectra

In the solar spectrum, CH vibration-rotation lines are excited to higher vibrational and much higher rotational quantum numbers than in any laboratory source. Observations were made, for the first time, of a very large number of new lines (1-0 and 2-1 up to J = 34.5, 3-2 up to J = 31.5, and even 4-3, never seen before, up to J = 24.5) on solar spectra obtained from space, with the ATMOS-SL3 instrument. A total of 558 lines have been used to derive new accurate molecular constants for the X 2Pi ground state of CH.

Melen, F.↗