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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 1,297 records · Page 72
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

A neural network-based approach to predicting absorption in nanostructured, disordered photoelectrodes

Disordered nanostructures in photoelectrodes can increase light absorption in photoelectrochemical system designs. Predicting their optical properties is an elusive task due to the immensity of unique configurations and the intrinsic variance of each. A neural network trained from a small subset of simulations can emulate the complex absorption properties of the entire configuration space for a model disordered system with quantifiable accuracy and computational efficiency.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Excited-state structural dynamics of nickel complexes probed by optical and X-ray transient absorption spectroscopies: insights and implications

Excited states of nickel complexes undergo a variety of photochemical processes, such as charge transfer, ligation/deligation, and redox reactions, relevant to solar energy conversion and photocatalysis. The efficiencies of the aforementioned processes are closely coupled to the molecular structures in the ground and excited states. The conventional optical transient absorption spectroscopy has revealed important excited-state pathways and kinetics, but information regarding the metal center, in particular transient structural and electronic properties, remains limited. These deficiencies are addressed by X-ray transient absorption (XTA) spectroscopy, a detailed probe of 3d orbital occupancy, oxidation state and coordination geometry. The examples of excited-state structural dynamics of nickel porphyrin and nickel phthalocyanine have been described from our previous studies with highlights on the unique structural information obtained by XTA spectroscopy. Furthermore, we close by surveying prospective applications of XTA spectroscopy to active areas of Ni-based photocatalysis based on the knowledge gained from our previous studies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Application of saturation absorption spectroscopy to study the hyperfine structure of 235U and accurate 235U/238U isotope ratio determinations at 861.031 nm

The uranium transition 5f 3 6d7s 2 ( 5 L 6 ) → 5f 3 7s 2 7p ( 5 K 5 ) at 861.031 nm was studied using saturation absorption spectroscopy. The hyperfine structure of the 235 U isotope was determined by measuring the Doppler-suppressed absorption spectrum, and the hyperfine structure constants were obtained by employing transition-specific line strength theory and spectral fitting. The magnetic-dipole and electric-quadrupole constants were determined to be A = -3.2887 ± 0.1957 mK and B = 31.8712 ± 8.0789 mK for the upper state 5f 3 7s 2 7p ( 5 K 5 ). A theoretical calculation for the hyperfine structure constants of the 235 U isotope was also carried out by the relativistic configuration-interaction (RCI) method, and the obtained values were found to be in agreement with the measured values. In addition, the line profile of 238 U was experimentally investigated for different excitation intensities and modeled using the RCI method for estimating the transition probability and oscillator strength, with various residual broadening mechanisms considered beyond the radiative decay. Finally, we show that these results allow us to make improvements on the precision of spectral measurements using our previously developed technique for isotope ratio determinations in atomic beams.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Revisiting the K-edge X-ray absorption fine structure of Si, Ge–Si alloys, and the isoelectronic series: CuBr, ZnSe, GaAs, and Ge

Extended X-ray absorption fine structure (EXAFS) has evolved into an unprecedented local-structure technique that is routinely used to study materials’ problems in the biological, chemical, and physical sciences. Like many other experimental techniques, EXAFS also requires that several key atomic parameters must be known a priori before structural information can be quantitatively determined. Utilizing current analytical methods, we revisit the isoelectronic series CuBr, ZnSe, GaAs, and Ge originally studied by Stern et al. during the early development of EXAFS. We demonstrate that the ab initio EXAFS code FEFF accurately predicts the atomic phase shifts and backscattering amplitudes that are primarily functions of the sum of atomic numbers Z along an EXAFS scattering path. We also investigate quantitative fitting and first- and second-shell phase transferability together with problems that arise if a backscattering atom is identified incorrectly in an EXAFS fitting model. Features in the near-edge region, on the other hand, are shown to require a comprehensive treatment of the band structure and density-of-states, including effects of the screened Coulomb interaction between the photoelectron and core hole. Here, we demonstrate that the Bethe–Salpeter equation (BSE) accurately captures the NEXAFS (or XANES) portion of the spectrum for the isoelectronic series in addition to Si and Ge–Si alloys, including within a few eV of the absorption edge, where band structure and excitonic effects are most important.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Towards a theoretical understanding of excitonic properties of phthalocyanine thin films. I. Low-temperature exciton absorption spectra

Phthalocyanine (Pc)-based molecular thin films have emerged in recent years as a promising class of organic semiconductor materials for optoelectronic applications owing to their long exciton coherence length and fast exciton diffusion. However, the dependence of their exciton properties on the dimensionality and thermodynamic conditions, presence of metal ions, and effects of chemical modifications to the PC systems is not yet fully understood. As a first step towards a more comprehensive theoretical understanding of the excitonic properties of Pc thin films, we model their low-temperature exciton absorption spectra by employing the Frenkel Hamiltonian. The latter is derived from quantum-chemical estimates of site energies and exciton–exciton couplings. The predicted exciton absorption spectra of octabutoxy phthalocyanine (H 2 OBPc) is found to be strongly dependent on the dimensionality of the model as well as the distance cutoff for including the monomer–monomer exciton coupling. We also caution that the widely used dipole–dipole approximation could substantially overestimate the excitonic coupling between different monomers compared to a more accurate evaluation using the respective transition densities.

36 MATERIALS SCIENCE↗
DOE OSTI2025

The electrode–electrolyte interface of Cu via modulation excitation X-ray absorption spectroscopy

The development and application of modulation excitation X-ray absorption spectroscopy with sub-second resolution and better than 0.02% detection sensitivity unveils the kinetics of the anodic oxidation of Cu in bicarbonate electrolytes. Accessing the electrode–electrolyte interface under operating conditions and capturing time-resolved kinetics remain challenging in electrochemical studies. Copper's interfacial oxidation dynamics remain unclear despite extensive research. Modulation excitation X-ray absorption spectroscopy (ME-XAS) was used to probe Cu in 100 mM KHCO 3 with sub-second sensitivity, revealing that hydroxide forms 30 ± 10 ms before the appearance of Cu 2 O at positive potentials (0 to 0.5 V vs. RHE) near open-circuit conditions. From −0.4 to 0.8 V vs. RHE, hydroxide coverage reaches 49%, accompanied by a balanced presence of Cu( i ) and Cu( ii ) oxides. These insights into Cu interfacial redox behavior under intermittent renewable energy operation—relevant to CO 2 electrolyzer durability—enhance our fundamental understanding of electrochemical interfaces.

Garcia-Esparza, Angel T↗
DOE OSTI2019

Baryon acoustic oscillations from the cross-correlation of Ly α absorption and quasars in eBOSS DR14

We present a measurement of the baryon acoustic oscillation (BAO) scale at redshift z =2.35 from the three-dimensional correlation of Lyman- α (Ly α ) forest absorption and quasars. The study uses 266 590 quasars in the redshift range 1.77< z < 3.5 from the Sloan Digital Sky Survey (SDSS) Data Release 14 (DR14). The sample includes the first two years of observations by the SDSS-IV extended Baryon Oscillation Spectroscopic Survey (eBOSS), providing new quasars and re-observations of BOSS quasars for improved statistical precision. Statistics are further improved by including Ly α absorption occurring in the Ly β wavelength band of the spectra. From the measured BAO peak position along and across the line of sight, we determined the Hubble distance D H and the comoving angular diameter distance D M relative to the sound horizon at the drag epoch r d : D H ( z =2.35)/ r d =9.20 ± 0.36 and D M ( z =2.35)/ r d =36.3±1.8. These results are consistent at 1.5 σ with the prediction of the best-fit spatially-flat cosmological model with the cosmological constant reported for the Planck (2016) analysis of cosmic microwave background anisotropies. Combined with the Ly α auto-correlation measurement presented in a companion paper, the BAO measurements at z =2.34 are within 1.7 σ of the predictions of this model.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2017

Simulating the absorption spectra of helium clusters (N = 70, 150, 231, 300) using a charge transfer correction to superposition of fragment single excitations

Simulations of the n = 2 absorption spectra of HeN(N = 70, 150, 231, 300) clusters are reported, with nuclear configurations sampled by path integral molecular dynamics. The electronic structure is treated by a new approach, ALMO-CIS+CT, which is a formulation of configuration interaction singles (CIS) based on absolutely localized molecular orbitals (ALMOs). The method generalizes the previously reported ALMO-CIS model [K. D. Closser et al. J. Chem. Theory Comput. 11, 5791 (2015)] to include spatially localized charge transfer (CT) effects. It is designed to recover large numbers of excited states in atomic and molecular clusters, such as the entire n = 2 Rydberg band in helium clusters. ALMO-CIS+CT is shown to recover most of the error caused by neglecting charge transfer in ALMO-CIS and has comparable accuracy to standard CIS for helium clusters. For the n = 2 band, CT stabilizes states towards the blue edge by up to 0.5 eV. ALMO-CIS+CT retains the formal cubic scaling of ALMO-CIS with respect to system size. With improvements to the implementation over that originally reported for ALMO-CIS, ALMO-CIS+CT is able to treat helium clusters with hundreds of atoms using modest computing resources. Here, a detailed simulation of the absorption spectra associated with the 2s and 2p bands of helium clusters up to 300 atoms is reported, using path integral molecular dynamics with a spherical boundary condition to generate atomic configurations at 3 K. The main features of experimentally reported fluorescence excitation spectra for helium clusters are reproduced.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

The importance of inner-shell electronic structure for enhancing the EUV absorption of photoresist materials

In order to increase computation power and efficiency, the semiconductor industry continually strives to reduce the size of features written using lithographic techniques. The planned switch to a shorter wavelength extreme ultraviolet (EUV) source presents a challenge for the associated photoresists, which in their current manifestation show much poorer photoabsorption cross sections for the same dose. Here we consider the critical role that an inner-shell electronic structure might play in enhancing photoabsorption cross sections, which one can control by the choice of substituent elements in the photoresist. In order to increase the EUV sensitivity of current photoresists, it is critical to consider the inner-shell atomic structure of the elements that compose the materials. We validate this hypothesis using a series of halogenated organic molecules, which all have similar valence structures, but differ in the character of their semi-core and deep valence levels. Using various implementations of time-dependent density functional theory, the absorption cross sections are computed for the model systems of CH3X, X = H, OH, F, Cl, Br, I, as well as a representative polymer fragment: 2-methyl-phenol and its halogenated analogues. Iodine has a particularly high cross section in the EUV range, which is due to delayed absorption by its 4d electrons. The computational results are compared to standard database values and experimental data when available. Generally we find that the states that dominate the EUV oscillator strength are generated by excitations of deep valence or semi-core electrons, which are primarily atomic-like and relatively insensitive to the specific molecular structure.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2017

Optical absorption and disorder in delafossites

Here, we present compelling experimental results of the optical characteristics of transparent oxide CuGaO 2 and related CuGa 1-x Fe x O 2 (with 0.00 ≤ x ≤ 0.05) alloys, whereby the forbidden electronic transitions for CuGaO 2 become permissible in the presence of B-site (Ga sites) alloying with Fe. Our computational structural results imply a correlation between the global strain on the system and a decreased optical absorption edge. However, herein, we show that the relatively ordered CuGa 1-x Fe x O 2 (for 0.00 ≤ x ≤ 0.04) structures exhibit much weaker vis-absorption compared to the relatively disordered CuGa 0.95 Fe 0.05 O 2 .

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2018

Attosecond transient absorption instrumentation for thin film materials: Phase transitions, heat dissipation, signal stabilization, timing correction, and rapid sample rotation

We present an extreme ultraviolet (XUV) transient absorption apparatus tailored to attosecond and femtosecond measurements on bulk solid-state thin-film samples, specifically when the sample dynamics are sensitive to heating effects. The setup combines methodology for stabilizing sub-femtosecond time-resolution measurements over 48 h and techniques for mitigating heat buildup in temperature-dependent samples. Single-point beam stabilization in pump and probe arms and periodic time-zero reference measurements are described for accurate timing and stabilization. A hollow-shaft motor configuration for rapid sample rotation, raster scanning capability, and additional diagnostics are described for heat mitigation. Heat transfer simulations performed using a finite element analysis allow comparison of sample rotation and traditional raster scanning techniques for 100 Hz pulsed laser measurements on vanadium dioxide, a material that undergoes an insulator-to-metal transition at a modest temperature of 340 K. Experimental results are presented confirming that the vanadium dioxide (VO 2 ) sample cannot cool below its phase transition temperature between laser pulses without rapid rotation, in agreement with the simulations. The findings indicate the stringent conditions required to perform rigorous broadband XUV time-resolved absorption measurements on bulk solid-state samples, particularly those with temperature sensitivity, and elucidate a clear methodology to perform them.

47 OTHER INSTRUMENTATION↗
DOE OSTI2018

Soft x-ray optical constants of sputtered chromium thin films with improved accuracy in the L and M absorption edge regions

In this paper, we determine with improved accuracy the complex index of refraction n = 1 - δ + iβ of sputtered chromium thin films for photon energies ranging from 25 eV to 813 eV. These data include the first absolute measurements of the absorption fine structure near the Cr-L edge. First, we verified by combining Rutherford Backscattering Spectrometry and grazing-incidence x-ray reflectometry that the sputtered thin films were pure Cr with a density consistent with tabulated values. Then, we demonstrated that the Cr surface oxide layer remains stable when the samples are exposed to air for up to 4 years. The Cr absorption coefficient β was determined from the transmittance of freestanding Cr thin films with various thicknesses, measured at the ALS synchrotron radiation source. A model is proposed to correct the transmittance data from the spectral contamination of the source. Finally, we used the new β values, combined with theoretical and tabulated data from the literature, in order to calculate the δ values by the Kramers-Kronig relation. The improvement in the accuracy of β values is demonstrated by the f-sum rule. Finally, an additional validation of the new Cr optical constants (δ, β) is performed by comparing the simulated and experimental reflectance of a Cr/B 4 C multilayer mirror near the Cr-L 2,3 edge.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Multiple striated heat fluxes patterns on the EAST first wall generated by lower hybrid wave absorption in the scrape-off layer

Multiple striated heat fluxes on the EAST first wall are observed with lower hybrid wave (LHW) heating on the EAST device. Our analysis indicates that the heat source for the striated heat flux is from LHW absorption in the scrape-off layer (SOL). Magnetic field line tracing from the front of the LHW antenna grills is in good agreement with the striated heat flux profile. In addition the relative intensity of the LHW absorption in the SOL is consistent with the measured striated heat flux. However, the heat flux at inner strike points and outer strike points significantly decreased when the ion cyclotron resonance frequency (ICRF) wave was switched off, while there was no change for the striated heat flux, suggests that the striated heat flux is independent on the injected power to the core plasma.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2019

Modeling L 2,3 -edge X-ray absorption spectroscopy with linear response exact two-component relativistic time-dependent density functional theory

X-ray absorption spectroscopy (XAS) is a powerful tool that can provide physical insights into element-specific chemical processes and reactivities. Although relativistic time-dependent density functional theory (TDDFT) has been previously applied to model the L-edge region in XAS, there has not been a more comprehensive study of the choices of basis sets and density functional kernels available for variational relativistic excited state methods. In this work, we introduce the implementation of the generalized preconditioned locally harmonic residual algorithm to solve the complex-valued relativistic TDDFT for modeling the L-edge X-ray absorption spectra. Further, we investigate the L 2,3 -edge spectra of a series of molecular complexes using relativistic linear response TDDFT with a hybrid iterative diagonalization algorithm. A systematic error analysis was carried out with a focus on the energetics, intensities, and magnitude of L 2 –L 3 splitting compared to experiments. Additionally, the results from relativistic TDDFT calculations are compared to those computed using other theoretical methods, and the multideterminantal effects on the L-edge XAS were investigated.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2019

Intrinsic shape of free carrier absorption spectra in 4H-SiC

Free carrier absorption spectra are measured along the different polarization directions with respect to the c-axis of 4H-SiC using ultrafast differential transmission spectroscopy. Probing of excited carrier spectra in an undoped material reveals intrinsic resonances within the conduction band. Widths of the detected resonance peaks are shown to be wider than their theoretical estimates and more comparable to the ones observed in a low doped material. Relative strength of the peaks, on the other hand, is shown to be nearly excitation independent in contrast to the doping induced absorption weakening for the same transitions in n-type samples. Finally, free carrier cross sections are extracted from the excitation dependency of the detected spectra and linked to the individual electron and hole contributions in the near infrared range.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2019

Electrical tuning of a terahertz quantum cascade laser based on detuned intersubband absorption

A mechanism to electrically tune the frequency of terahertz quantum cascade lasers (QCLs) is developed that allows for tuning, while the QCL is operated close to its peak bias and temperature. Two optically coupled but electrically isolated cavities are used in which the bias of a control cavity tunes the resonant-mode of the coupled QCL cavity independent of the QCL's operating bias. Approximately 4 GHz electrical tuning is realized for a 3.6 THz distributed-feedback QCL operating in pulsed mode at 58 K in a Stirling cooler. The single-mode QCL emits near-constant peak-power in the range of 5$-$5.3 mW through the tuning range and radiates in a narrow single-lobed beam with a far-field divergence of ~4°×11°. The superlattice structure of the QCL is designed to implement a low-voltage intersubband absorption transition that is detuned from that of its gain transition, the strength of which could be controlled sensitively with applied voltage utilizing resonant-tunneling injection of electrons in the absorption subband. Finally, the tuning is realized by the application of small bias voltages (~6$-$7 V) and requires a narrow bias range (~1 V, ~40 A/cm 2 ) to traverse across the entire tuning range, and the method should be generally applicable to all intersubband lasers including mid-infrared QCLs.

42 ENGINEERING↗
DOE OSTI2025

Time-resolved x-ray absorption spectroscopy probe in ultrafast surface chemistry

To celebrate the scientific achievement of Jo Stöhr, I present here a personal account of the use of x-ray absorption spectroscopy to probe dynamics on surfaces using x-ray lasers. In particular, I will review the investigation of ultrafast processes in adsorbates on surfaces using an optical pump and an x-ray absorption spectroscopy probe. Here, it is shown that it is possible to gain insight into the effects of electronic excitations in metals on adsorbates as well as laser-induced vibrational motions. Furthermore, the ultrafast optical pump allows the detection of the CO precursor state in the desorption channel, species close to the transition state in CO oxidation, and the transient HCO intermediate during CO hydrogenation on Ru(0001).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Cavity molecular dynamics simulations of vibrational polariton-enhanced molecular nonlinear absorption

We report recent experiments have observed that the chemical and photophysical properties of molecules can be modified inside an optical Fabry– Pérot microcavity under collective vibrational strong coupling (VSC) conditions, and such modification is currently not well understood by theory. In an effort to understand the origin of such cavity-induced phenomena, some recent studies have focused on the effect of the cavity environment on the nonlinear optical response of the molecular subsystem. Here, we use a recently proposed protocol for classical cavity molecular dynamics simulations to numerically investigate the linear and the nonlinear response of liquid carbon dioxide under such VSC conditions following an optical pulse excitation. We find that applying a strong pulse of excitation to the lower hybrid light–matter state, i.e., the lower polariton (LP), can lead to an overall molecular nonlinear absorption that is enhanced by up to two orders of magnitude relative to the excitation outside the cavity. This polariton-enhanced multiphoton absorption also causes an ultrashort LP lifetime (0.2 ps) under strong illumination. Unlike usual polariton relaxation processes—whereby polaritonic energy transfers directly to the manifold of singly excited vibrational dark states—under the present mechanism, the LP transfers energy directly to the manifold of higher vibrationally excited dark states; these highly excited dark states subsequently relax to the manifold of singly excited states with a lifetime of tens of ps. Because the present mechanism is generic in nature, we expect these numerical predictions to be experimentally observed in different molecular systems and in cavities with different volumes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗