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At least 307 records · Page 17

Infrared spectroscopy data- and physics-driven machine learning for characterizing surface microstructure of complex materials

There is a need to characterize complex materials and their dynamics under reaction conditions to accelerate materials design. Adsorbate vibrational excitations are selective to adsorbate/surface interactions and infrared (IR) spectra associated with activating adsorbate vibrational modes are accurate, capture details of most modes, and can be obtained operando. Current interpretation depends on heuristic peak assignments for simple spectra, precluding the possibility of obtaining detailed structural information. Here, we combine data-based approaches with chemistry-dependent problem formulation to develop physics-driven surrogate models that generate synthetic IR spectra from first-principles calculations. Using synthetic IR spectra of carbon monoxide on platinum, we implement multinomial regression via neural network ensembles to learn probability distributions functions (pdfs) that describe adsorption sites and quantify uncertainty. We use these pdfs to infer detailed surface microstructure from experimental spectra and extend this methodology to other systems as a first step towards characterizing complex interfaces and closing the materials gap.

Science & Technology - Other Topics↗

Properties of giant dipole resonances within an extended pairing model with a focus on spectral statistics

In this paper, we report on a study of the spectral features associated with dipole resonances in medium mass nuclei (E ≤ 12 MeV), as revealed in the framework of the spd-interacting boson model. The effect of pairing correlations on the theory follows from solutions obtained through an application of the Bethe Ansatz Equation. In general, calculated spectra around the critical point of the vibrational to γ-soft transitions appears to approach that of a Gaussian Orthogonal Ensemble, while near the rotational and vibrational limits of the theory the spectra show more regular behavior. Specifically, the results reveal that the statistical features of the spectra are sensitive to the vector boson pairing strength, c p , in the transition region; that is, when c p is zero, or when the system approaches one of its dynamical symmetries limits the spectrum display regular features, while for stronger c p values, or when near to the critical phase transition region, the spectral feature show more chaotic behavior. Overall, our results indicate that the statistical features are governed by the interplay between dipole resonant energies, pairing correlations, and interactions between and among the single and vector bosons modes of the theory. As part of this work we also found out that chaoticity occurs when results were fit to a Berry-Robnik distribution. Throughout our analyses, we used experimentally known information about both positive and negative parity states. Our findings suggest that dipole resonances appear to be best-described by Poisson statistics for A ≈ 32-138 nuclei.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

High-resolution near-infrared spectroscopy of water dimer

High-resolution near-infrared spectra are reported for all of the O-H stretch vibrational bands of the water dimer. The four O-H vibrations are characterized as essentially independent proton-donor or proton-acceptor motions. In addition to the rotational and vibrational information contained in these spectra, details are obtained concerning the internal tunneling dynamics in both the ground and excited vibrational states. These results show that, for tunneling motions which involve the interchange of the proton donor and acceptor molecules, the associated frequencies decrease substantially due to vibrational excitation. The predissociation lifetimes for the various states of the dimer are determined from linewidth measurements. These results clearly show that the predissociation dynamics is strongly dependent on the tunneling states, as well as the Ka quantum number, indicating that the internal tunneling dynamics plays an important role in determining the dissociation rate in this complex.

Huang, Z. S.↗

Simulations of the IR and Raman spectra of water confined in amorphous silica slit pores

Water in nano-scale confining environments is a key element in many biological, material, and geological systems. The structure and dynamics of the liquid can be dramatically modified under these conditions. Probing these changes can be challenging, but vibrational spectroscopy has emerged as a powerful tool for investigating their behavior. A critical, evolving component of this approach is a detailed understanding of the connection between spectroscopic features and molecular-level details. In this paper, this issue is addressed by using molecular dynamics simulations to simulate the linear infrared (IR) and Raman spectra for isotopically dilute HOD in D 2 O confined in hydroxylated amorphous silica slit pores. The effect of slit-pore width and hydroxyl density on the silica surface on the vibrational spectra is also investigated. The primary effect of confinement is a blueshift in the frequency of OH groups donating a hydrogen bond to the silica surface. This appears as a slight shift in the total (measurable) spectra but is clearly seen in the distance-based IR and Raman spectra. Analysis indicates that these changes upon confinement are associated with the weaker hydrogen-bond accepting properties of silica oxygens compared to water molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Vibrational populations of O sub 2

Herzberg bands synthetic spectra matched to various spectrograms to determine vibrational populations of molecular O state in nightglow

Degen, V.↗

Response measurements for two building structures excited by noise from a large horizontal axis wind turbine generator

Window and wall acceleration measurements and interior noise measurements ere made for two different building structures during excitation by noise from the WTS-4 horizontal axis wind turbine generator operating in a normal power generation mode. With turbine noise input pulses resulted in acceleration pulses for the wall and window elements of the two tests buildings. Response spectra suggest that natural vibration modes of the structures are excited. Responses of a house trailer were substantially greater than those for a building of sturdier construction. Peak acceleration values correlate well with similar data for houses excited by flyover noise from commercial and military airplanes and helicopters, and sonic booms from supersonic aircraft. Interior noise spectra have peaks at frequencies corresponding to structural vibration modes and room standing waves; and the levels for particular frequencies and locations can be higher than the outside levels.

Hubbard, H. H.↗

Wavelength-resolved emission spectroscopy of the alkoxy and alkylthio radicals in a supersonic jet

Wavelength-resolved emission spectra of methoxy (CH3O) and methylthio (CH3S) radicals have been obtained in a supersonic jet environment with a resolution of 0.3 nm by dispersing the total laser-induced fluorescence with a 0.6 m monochromator. A detailed analysis of the single vibronic level dispersed fluorescence spectra yields the following vibrational frequencies for CH3O in the X(2)E state; nu(sub 1 double prime) = 2953/cm, nu(sub 2 double prime) = 1375/cm, nu(sub 3 double prime) = 1062/cm, nu(sub 4 double prime) = 2869/cm, nu(sub 5 double prime) = 1528/cm and nu(sub 6 double prime) = 688/cm. A similar analysis of the wavelength-resolved emission spectra of CH3S provides the following ground state vibrational frequencies: nu(sub 2 double prime) = 1329/cm, nu(sub 3 double prime) = 739/cm and nu(sub 6 double prime) = 601/cm. An experimental uncertainty of 20/cm is estimated for the assigned frequencies.

Misra, Prabhakar↗

Vibrational spectroscopy of uranium tetrafluoride hydrates

Uranium tetrafluoride (UF 4 ) is an important intermediate in the production of UF6 and nuclear fuel. Historical characterization of UF 4 with Raman spectroscopy was plagued with ambiguity until the first accurate Raman spectrum was published by our group in 2016. Although generally considered to be relatively stable, UF 4 can hydrolyze to form numerous UF 4 hydrates that may play a role in future uranium waste forms. In contrast to anhydrous UF 4 , the hydrates, with their OH stretch and HOH bending modes, can be spectroscopically characterized by the type and degree of water bonding in the crystal lattice, which can yield additional information about their crystal structure. Herein, vibrational spectroscopy (Raman and infrared) was used to characterize three different UF 4 hydrates: UF 4 (H 2 O) 0.33 , U 3 F 12 (H 2 O), and UF 4 (H 2 O) 2.5 . Spectra show the different hydrates vary in the number of observed bands, full-width half-maximum of the bands, and band intensity. These differences are due to varying interactions between the OH stretch and HOH bending modes with UF 4 and the polymeric UF 4 structure in the crystal lattice. These vibrational data, in combination with spectral fitting and crystallographic structures measured with powder X-ray diffraction and single crystal X-ray diffraction, provide unique details on the location of water molecules in the crystal lattice of hydrated UF 4 , and provide an interesting contrast to the vibrational spectra of anhydrous UF 4 .

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

An experimental and computational investigation of the structure and spectroscopic signatures of α -UO 3

α-UO 3 is a common intermediate compound found in the nuclear fuel cycle, yet the exact crystal structure of this material has long been debated. Inconsistent computational and experimental data in previous works has led to varying conclusions between authors. Furthermore, to ensure the validity of our results in this work, the structural and spectroscopic signatures of pure phase α-UO 3 are investigated using powder X-ray diffraction and optical vibrational spectroscopy (infrared and Raman). Rietveld refinement of powder X-ray diffraction data on pure phase α-UO 3 collected in this work allows us to propose an alteration to the currently accepted C2mm structure (a = 3.9705 Å, b = 6.8553 Å, c = 4.15955 Å, α = β = γ = 90°) for α-UO 3 with no uranyl [UO 2 2+ ] bonds. Raman spectra collected using two excitation wavelengths (two instruments using 532 nm and one 785 nm) are presented, and differences with recently published results are discussed. Infrared spectra from two instruments used here agree well with recently published results, but the spectral range encompassed in our data extends past what has been reported with modern techniques. Additionally, we provide tentative vibrational mode assignments based on density functional perturbation theory calculations and resulting phonon eigenvector visualizations. Unexpected features in the optical vibrational spectra of α-UO 3 are explained by unique features in the structure we present.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Spontaneous Raman Scattering Diagnostics for High-pressure Gaseous Flames

A high-pressure (up to 60 atm) gaseous burner facility with optical access that provides steady, reproducible flames with high precision, and the ability to use multiple fuel/oxidizer combinations has been developed. In addition, a high-performance spontaneous Raman scattering system for use in the above facility has also been developed. Together, the two systems will be used to acquire and establish a comprehensive Raman scattering spectral database for use as a quantitative high-pressure calibration of single-shot Raman scattering measurements in high-pressure combustion systems. Using these facilities, the Raman spectra of H2-Air flames were successfully measured at pressures up to 20 atm. The spectra demonstrated clear rotational and ro-vibrational Raman features of H2, N2, and H2O. theoretical Raman spectra of pure rotational H2, vibrational H2, and vibrational N2 were calculated using a classical harmonic-oscillator model with pressure broadening effects and fitted to the data. At a gas temperature of 1889 K for a phi = 1.34 H2-Air flame, the model and the data showed good agreement, confirming a ro-vibrational equilibrium temperature.

Kojima, Jun↗

First-Principles Treatment of Vibrational Broadening in X-Ray Excited Valence Band Spectra for n-SrTiO 3 (001)

The valence band maximum (VBM) is an important quantity for semiconductors as it locates the Fermi level relative to the band edge. Accurate measurement of this quantity in near-surface regions of semiconductors by photoemission is a first step toward determining the electronic properties of heterostructures involving these materials. While extrapolating the leading edge of the valence band to the energy axis in photoemission spectra is a widely used way to find the VBM, this method can be ambiguous if the leading edge exhibits multiple slopes. Another way to determine the VBM is to fit the leading edge to an appropriately broadened, cross-section modulated theoretical density of states (DOS). Three kinds of broadening that should be included for maximum accuracy are those due to: (1) finite instrumental resolution, (2) valence hole lifetime, and (3) vibrational excitations. While steps (1) and (2) are straightforward to implement, (3) is more difficult because the appropriate amount of broadening is not known a priori. Here, we demonstrate that explicit inclusion of vibrational broadening using ab initio molecular dynamics facilitates accurate VBM determination for n-SrTiO 3 (001). The total DOS is constructed by summing time-averaged projections at elevated temperature onto s - , p - , and d orbitals for the constituent atoms and modulating with the associated photoemission cross sections. Subsequent convolutions of the total DOS, first with a Gaussian of width equal to the experimental energy resolution and second with a Lorentzian to simulate valence hole lifetime effects, yield line shapes that reproduce the experimental leading edges rather well. The VBM is then given by the energy at which the vibrationally broadened total DOS (prior to the convolutions) goes to zero. The VBMs generated by this method quantitatively agree with those resulting from extrapolating from the middle of the measured leading edge for SrTiO 3 .

36 MATERIALS SCIENCE↗

Database of low‐temperature absorption and fluorescence spectra of native photosynthetic tetrapyrrole macrocycles

Low-temperature (77 K) absorption and fluorescence spectra of 12 naturally occurring photosynthetic tetrapyrrole macrocycles have been recorded in a frozen glass (2-methyltetrahydrofuran). The compounds encompass distinct chromophore classes: porphyrin, chlorophyll c 2 ; chlorin, chlorophylls a, b, d, f and bacteriochlorophylls c, d, e, f; and bacteriochlorin, bacteriochlorophylls a, b, g. The spectra are compared with those of the same pigment in liquid solution (predominantly 2-methyltetrahydrofuran) at room temperature (293 K). The measured Stokes shifts at 77 K across the 12 macrocycles range from ~30 to 300 cm −1 . The spectral data in digital form are made available as part of the PhotochemCAD databases. Literature searches have revealed extensive published data for Chl a (often in biological matrices) but at best rather limited data for less common macrocycles. The availability of a systematic collection of curated spectral data collected at low temperature should be useful for a variety of assessments, including reconstruction of absorption spectra of (bacterio)chlorophyll-containing protein complexes, vibrational analysis of absorption and fluorescence spectra, and calculations where knowledge of energy levels is important.

Niedzwiedzki, Dariusz M. [Washington University in↗

The nu(sub 2) and 2nu(sub 2) - nu(sub 2) bands of N-14 (16)O2: Electron Spin-Rotation and Hyperfine Contact Resonances in the (010) Vibrational State

High-resolution Fourier transform spectra covering the 720-9-10/ cm spectral region have been used to perform a reanalysis of the 2nu(sub 2) band ((010) - (000) vibrational transition) together with the first analysis of the nu(sub 2) - nu(sub 2) hot band of nitrogen dioxide ((020)-(010) vibrational transition). The high-quality spectra show that, for numerous nu(sub 2) lines, the hyperfine structure is easily observable in the case of resonances due to the hyperfine Fermi-type operator. By performing a full treatment of the spin-rotation and of the hyperfine operators, a near line list of the nu(sub 2) band (positions and intensities) has been generated, and it is in excellent agreement with the experimental spectrum. Also, a thorough analysis of the -2nu(sub 2) nu(sub 2) hot band has been performed leading to an extended set of new (020) spin-rotation levels, These levels, together with the (100), (020), (001) spin-rotation levels deduced previously from the analysis of thenu(sub 1), 2nu(sub 2), and nu(sub 3) cold bands performed in the 6.3 - to 7.5 microns spectral range were least-squares fitted, allowing one to derive a new set of vibrational band centers and rotational. spin-rotation, and interaction constants for the {(100)(020)(001)} interacting states of N-14(16)O2.

Perrin, A.↗

Measurements of self-excited rotor-blade vibrations using optical dispacements

The characteristics of optical displacement spectra and their role of monitoring rotor blade vibrations are discussed. During the operation of a turbofan engine at part speed, near stall, and elevated inlet pressure and temperature, several vibratory instabilities were excited simultaneously on the first fan rotor. The torsional and bending contributions to the main flutter mode were resolved by using casing-mounted optical displacement sensors. Other instabilities in the blade deflection spectra were identified.

Kurkov, A. P.↗

Measurements of self-excited rotor-blade vibrations using optical displacements

The characteristics of optical displacement spectra and their role of monitoring rotor blade vibrations are discussed. During the operation of a turbofan engine at part speed, near stall, and elevated inlet pressure and temperature, several vibratory instabilities were excited simultaneously on the first fan rotor. The torsional and bending contributions to the main flutter mode were resolved by using casing-mounted optical displacement sensors. Other instabilities in the blade deflection spectra were identified. Previously announced in STAR as N83-14523

Kurkov, A. P.↗

Isomers and band assignments in the cryogenic vibrational spectrum of the binary complex between water and protonated formic acid using two color, IR–IR photobleaching and H/D isotopic substitution

Protonated formic acid (PFA) is purported to be the active species in the catalytic activation of condensation reactions at the acidic interface of microdroplets. Here, we investigate the fundamental interaction between PFA and water with cryogenic ion vibrational spectroscopy of the binary PFA–H 2 O complexes generated via electrospray ionization followed by buffer gas cooling to about 20 K. The patterns displayed by the isomer-specific IR spectra of D 2 -tagged PFA–H 2 O indicate that two distinct, non-interconverting rotamers are present at low temperatures based on the cis and trans structures of the HCO 2 $H$$^{+}_{2}$ core ion. Both of these occur with the water molecule attached to the OH that is in a cis-configuration relative to the CH group (denoted E), but differ in the E vs Z (cis vs trans relative to the CH group) orientation of the spectator OH. This assignment scheme corrects a previous theoretical analysis that invoked a scenario in which structures with E- and Z-bound water molecules interconvert at low (20 K) temperatures. Isomer-specific bands arising from the OH stretches and water bending modes are deconvoluted using isotopomer-specific spectroscopy of the complexes with partial H/D exchange. The dependence of the nominal shared proton OH stretch frequency on the deuteration of the tethered water confirms strong coupling between this mode and the water bending fundamental.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

On the multiplicity of solutions of the inverse problem for a vibrating beam

The paper considers a specific inverse problem for a vibrating beam with three nonsympathetic spectra. More specifically, the spectral data consist of the natural frequencies of vibration of the beam in the following three configurations: (1) clamped-clamped, (2) clamped-supported, and (3) clamped-free. The basic equations for an inhomogeneous discrete beam are derived, where this simple mechanical system provides valuable insight into the inverse problem. All the necessary ingredients for a consideration of the inverse problem are given. Attention is given to an analysis of the particular inverse problem for which the spectral data are associated with the natural frequencies of vibrations in the above configurations. It is shown that with such data, the inverse problem has a 2exp(N-1)-fold multiplicity of solutions.

Barcilon, V.↗

Identification of the nu-2 vibration-rotation band of ammonia in ground level solar spectra

Comparison of infrared solar spectra in the 750 to 950 kayser region obtained during sunrise and sunset shows that a number of features due to the nu-2 NH3 band are present on the sunset spectra but are indicated by only a trace on the sunrise spectra. The sunset path shows approximately 0.007 atm-cm NH3, and the reason for the discrepancy between sunrise and sunset spectra is not known. The ground-based measurements at Denver were obtained with a 0.06 kayser resolution.

Murcray, D. G.↗