Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Vibrational Spectroscopy”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
NASA NTRS1993

Thermal-infrared emission spectroscopy of natural surfaces: Application to coated surfaces

Thermal-infrared vibrational spectroscopy has great potential for remotely determining the composition of planetary surface materials by taking advantage of fundamental molecular vibrational modes that produce spectral features in the range from approximately 3 to greater than 50 microns. Much of the current interest in the thermal infrared wavelength region stems from the deployment of multispectral scanners, such as the Thermal Infrared Multispectral Scanner (TIMS) and the Mars Observer Thermal Emission Spectrometer (TES). In order to support these missions, it is necessary to develop an appropriate library of laboratory measurements. The purpose of this work was to develop a technique which, with a very limited set of assumptions, can be used to determine the emissivity of natural surfaces directly by using emitted energy.

Christensen, Philip R.↗
DOE OSTI2024

The development and applications of multidimensional biomolecular spectroscopy illustrated by photosynthetic light harvesting

The parallel and synergistic developments of atomic resolution structural information, new spectroscopic methods, their underpinning formalism, and the application of sophisticated theoretical methods have led to a step function change in our understanding of photosynthetic light harvesting, the process by which photosynthetic organisms collect solar energy and supply it to their reaction centers to initiate the chemistry of photosynthesis. The new spectroscopic methods, in particular multidimensional spectroscopies, have enabled a transition from recording rates of processes to focusing on mechanism. We discuss two ultrafast spectroscopies – two-dimensional electronic spectroscopy and two-dimensional electronic-vibrational spectroscopy – and illustrate their development through the lens of photosynthetic light harvesting. Both spectroscopies provide enhanced spectral resolution and, in different ways, reveal pathways of energy flow and coherent oscillations which relate to the quantum mechanical mixing of, for example, electronic excitations (excitons) and nuclear motions. The new types of information present in these spectra provoked the application of sophisticated quantum dynamical theories to describe the temporal evolution of the spectra and provide new questions for experimental investigation. While multidimensional spectroscopies have applications in many other areas of science, we feel that the investigation of photosynthetic light harvesting has had the largest influence on the development of spectroscopic and theoretical methods for the study of quantum dynamics in biology, hence the focus of this review. We conclude with key questions for the next decade of this review.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Optical Spectroscopic Investigation of Hexavalent Actinide Ions in n-Dodecane Solutions of Tri-butyl Phosphate

The extraction of hexavalent actinides An(VI) by tri-butyl phosphate (TBP) was investigated by electronic absorption and vibrational spectroscopies. Through a series of spectral subtractions, vibrational spectra associated with TBP, TBP–HNO3 adducts, and An(VI)–TBP complexes could be isolated. Investigation of U(VI) extracts indicated spectral features consistent with the formation of the expected [UO2(NO3)2(TBP)2] complex, but spectral features of other species were clearly evident. Likewise, multiple species were evident in the electronic absorption and vibrational spectra of TBP phases generated by extraction of Pu(VI). Although definitive characterization of the additional species formed could not be achieved in this work, it is hypothesized that they contain 3:1 TBP-to-An(VI) stoichiometry.

Lumetta, Gregg J.↗
DOE OSTI2025

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↗
DOE OSTI2026

A foundation model for non-destructive defect identification from vibrational spectra

Defects are ubiquitous in solids and strongly influence materials’ functional properties. However, non-destructive characterization and quantification of defects, especially when multiple types coexist, remain a long-standing challenge. Here, we introduce DefectNet, a foundation machine learning model that predicts the chemical identity and concentration of substitutional point defects with multiple coexisting elements directly from vibrational spectra, specifically phonon density-of-states (PDoS). Trained on over 16,000 simulated spectra from 2,000 semiconductors, DefectNet employs a tailored attention mechanism to identify up to six distinct defect elements at concentrations ranging from 0.2% to 25%. The model generalizes well to unseen crystals across 56 elements and can be fine-tuned on experimental data. Validation using inelastic scattering measurements of SiGe alloys and MgB 2 superconductor demonstrates its accuracy and transferability. Furthermore, our work establishes vibrational spectroscopy as a viable, non-destructive probe for bulk point defect quantification, and highlights the promise of foundation models in data-driven defect engineering.

artificial intelligence↗
DOE OSTI2021

Simulation and analysis of slip flow of water at hydrophobic silica surfaces of nanometer slit pores

Water flow in nanopores is controlled fundamentally by pore wettability and interfacial water features. In the research herein reported, Molecular dynamics (MD) was used to simulate water flow in nanometer slit pores of silica surfaces with variable wetting characteristics. Compared to Couette flow, the simulated slit-pores of the talc (001) and octadecyltrichlorosilane (OTS) monolayer surfaces exhibited water flow enhancement and a positive slip length at the interface, whereas water flow velocity at the quartz (001) and amorphous silica surfaces was zero, adhering to the no slip condition. More intensive interactions between the interfacial water and hydrophilic silica surfaces were confirmed by MD simulation and sum-frequency vibrational spectroscopy (SFVS) results. A water exclusion zone of approximately 3 Å was found at the hydrophobic silica surfaces by quantitative MD interfacial water analysis and validated by SFVS. This exclusion zone dimension was similar in magnitude to the slip length (4–5 Å) as determined from simulated water flow in hydrophobic silica slit pores. The simulated slip lengths at the hydrophobic surfaces (0.2–1 nm) were significantly less than the experimental slip lengths (>40 nm) reported in the literature. In the case of the experimental results, this difference appears to be due to nanobubbles expected to be present at hydrophobic surfaces.

42 ENGINEERING↗
DOE OSTI2024

Evaluation of Aliphatic Alcohols for CO 2 Capture Using the Characteristic Carbonate Frequency

Control over CO 2 capture and utilization are important scientific and technological challenges. Although a variety of amine absorbents are used for capture, releasing the captured CO 2 is often difficult and limits their recyclability. Therefore, it is crucial to control the strength of the CO 2 bond with the absorbent. Furthermore, it is desirable to use a method that can conveniently report the strength of this bond. This motivates exploring adducts of CO 2 with alcohols in the presence of a base, using vibrational spectroscopy to report on the bond strength. Although reactions of alcohols with CO 2 to form alkyl carbonates are known, a systematic study of these adducts has not been conducted. Here we show formation of alkyl carbonates by a series of alcohols spanning the pK a range 9.5 to 16.8. We show experimental and computational results for the frequency of the characteristic asymmetric stretch of the carbonate and demonstrate that it correlates inversely with the pK a of the alcohol. Based on computations of the bond lengths and previous work, we propose that this frequency also correlates inversely with the adduct strength. As a result, this work extends the scope of CO 2 capture reagents and inspires further research in tuning alcohols as reversible absorbents.

Alcohols↗
DOE OSTI2025

Infrared spectral signatures of interfacial water at TiO 2 –electrolyte interfaces from deep potential molecular dynamics

Vibrational spectroscopy is a powerful tool for probing water at oxide–electrolyte interfaces, but its molecular interpretation can be challenging. Here, we employ deep potential long-range molecular dynamics simulations with layer-resolved spectral analysis to investigate the microscopic origins of the infrared (IR) response of water at the interface with anatase TiO 2 (101), a prototypical oxide surface. The calculated interfacial spectra exhibit characteristic modifications compared to bulk water IR spectra, including enhanced intensities, a red shifted and broadened stretching band, and a higher-frequency shoulder, in qualitative agreement with experiments. Spectral decomposition shows that these signatures originate mainly from the first interfacial water layer, dominated by surface-bound H 2 O at Ti 5C sites, with secondary contributions from the second layer. A moderate salt concentration (0.4 M NaCl) leaves both the interfacial structure and the spectra essentially unchanged, while tuning the pH strongly modulates the spectral intensity. We establish a scaling relation linking the spectral intensity to the surface water dissociation fraction and the dipole moment, both governed by interfacial electric fields. These findings provide a microscopic framework for interpreting IR spectra of oxide–electrolyte interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Deciphering the local structure of Prussian blue analogue cathodes with Raman spectroscopy for sodium-ion batteries

Iron-based Prussian blue analogues (PBAs) have gained attention as low-cost, relatively higher-potential cathodes for sodium-ion batteries, due to their open 3D-framework structures. However, understanding the local structural changes is critical to unveiling the intercalation pathways and degradation mechanisms. We employ here operando Raman spectroscopy to probe the changes in the cyanide vibrational modes during cycling and degradation after cycling, which are not adequately resolved by X-ray diffraction due to the low structure factor and limited X-ray sensitivity of the cyanide groups. Vibrational spectroscopy has thus proven essential for deciphering these complex materials. Additionally, we implement pre-sodiation strategies to assess the impact of sodium inventory loss by pairing PBAs with a hard carbon anode in a full-cell configuration. Operando galvanostatic electrochemical impedance spectroscopy (EIS) and ex situ X-ray photoelectron spectroscopy (XPS) further elucidate the interface evolution and the role of water molecules in forming the cathode-electrolyte interphase (CEI) and solid-electrolyte interphase (SEI). The insights gained advance the understanding of PBAs and enhance their practical viability.

25 ENERGY STORAGE↗
DOE OSTI2022

Structural and dynamic effects of paraoxon binding to human acetylcholinesterase by X-ray crystallography and inelastic neutron scattering

Organophosphorus (OP) compounds, including nerve agents and some pesticides, covalently bind to the catalytic serine of human acetylcholinesterase (hAChE), thereby inhibiting acetylcholine hydrolysis necessary for efficient neurotransmission. Oxime antidotes can reactivate the OP-conjugated hAChE, but reactivation efficiency can be low for pesticides, such as paraoxon (POX). Understanding structural and dynamic determinants of OP inhibition and reactivation can provide insights to design improved reactivators. Here, in this study, X-ray structures of hAChE with unaged POX, with POX and oximes MMB4 and RS170B, and with MMB4 are reported. A significant conformational distortion of the acyl loop was observed upon POX binding, being partially restored to the native conformation by oximes. Neutron vibrational spectroscopy combined with molecular dynamics simulations showed that picosecond vibrational dynamics of the acyl loop soften in the ~20–50 cm –1 frequency range. The acyl loop structural perturbations may be correlated with its picosecond vibrational dynamics to yield more comprehensive template for structure-based reactivator design.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Infrared compatible rapid mixer to probe millisecond chemical kinetics

Fast microfluidic mixers are a valuable tool for studying solution-phase chemical reaction kinetics and molecular processes with spectroscopy. However, microfluidic mixers that are compatible with infrared vibrational spectroscopy have seen only limited development due to the poor infrared transparency of the current microfabrication material. We describe the design, fabrication, and characterization of CaF2-based continuous flow turbulent mixers, which are capable of measuring kinetics in the millisecond time window with infrared spectroscopy, when integrated into an infrared microscope. Kinetics measurements demonstrate the ability to resolve relaxation processes with 1 millisecond time resolution, and straightforward improvements are described that should result in sub-100 µs time-resolution.

Instruments & Instrumentation↗
DOE OSTI2021

AFM-IR and s-SNOM-IR measurements of chemically addressable monolayers on Au nanoparticles

The performance of catalysts depends on their nanoscale properties, and local variations in structure and composition can have a dramatic impact on the catalytic reactivity. Therefore, probing the localized reactivity of catalytic surfaces using high spatial resolution vibrational spectroscopy, such as infrared (IR) nanospectroscopy and tip-enhanced Raman spectroscopy, is essential for mapping their reactivity pattern. Two fundamentally different scanning probe IR nanospectroscopy techniques, namely, scattering-type scanning near-field optical microscopy (sSNOM) and atomic force microscopy-infrared spectroscopy (AFM-IR), provide the capabilities for mapping the reactivity pattern of catalytic surfaces with a spatial resolution of ~20 nm. Herein, we compare these two techniques with regard to their applicability for probing the vibrational signature of reactive molecules on catalytic nanoparticles. For this purpose, we use chemically addressable self-assembled molecules on Au nanoparticles as model systems. We identified significant spectral differences depending on the measurement technique, which originate from the fundamentally different working principles of the applied methods. While AFM-IR spectra provided information from all the molecules that were positioned underneath the tip, the s-SNOM spectra were more orientation-sensitive. Due to its field-enhancement factor, the s-SNOM spectra showed higher vibrational signals for dipoles that were perpendicularly oriented to the surface. The s-SNOM sensitivity to the molecular orientation influenced the amplitude, position, and signal-to-noise ratio of the collected spectra. Ensemble-based IR measurements verified that differences in the localized IR spectra stem from the enhanced sensitivity of s-SNOM measurements to the adsorption geometry of the probed molecules.

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

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↗
NASA NTRS2008

Liquid Space Lubricants Examined by Vibrational Micro-Spectroscopy

Considerable effort has been expended to develop liquid lubricants for satellites and space exploration vehicles. These lubricants must often perform under a range of harsh conditions such as vacuum, radiation, and temperature extremes while in orbit or in transit and in extremely dusty environments at destinations such as the Moon and Mars. Historically, oil development was guided by terrestrial application, which did not provide adequate space lubricants. Novel fluids such as the perfluorinated polyethers provided some relief but are far from ideal. With each new fluid proposed to solve one problem, other problems have arisen. Much of the work performed at the National Aeronautics and Space Administration (NASA) Glenn Research Center (GRC) in elucidating the mechanisms by which chemical degradation of space oils occur has been done by vibrational micro-spectroscopic techniques such as infrared and Raman, which this review details. Presented are fundamental lubrication studies as well as actual case studies in which vibrational spectroscopy has led to millions of dollars in savings and potentially prevented loss of mission.

Street, Kenneth W., Jr.↗
DOE OSTI2024

Decoupling excitons from high-frequency vibrations in organic molecules

The coupling of excitons in π-conjugated molecules to high-frequency vibrational modes, particularly carbon–carbon stretch modes (1,000–1,600 cm -1 ) has been thought to be unavoidable. These high-frequency modes accelerate non-radiative losses and limit the performance of light-emitting diodes, fluorescent biomarkers and photovoltaic devices. Here, by combining broadband impulsive vibrational spectroscopy, first-principles modelling and synthetic chemistry, we explore exciton–vibration coupling in a range of π-conjugated molecules. We uncover two design rules that decouple excitons from high-frequency vibrations. First, when the exciton wavefunction has a substantial charge-transfer character with spatially disjoint electron and hole densities, we find that high-frequency modes can be localized to either the donor or acceptor moiety, so that they do not significantly perturb the exciton energy or its spatial distribution. Second, it is possible to select materials such that the participating molecular orbitals have a symmetry-imposed non-bonding character and are, thus, decoupled from the high-frequency vibrational modes that modulate the π-bond order. We exemplify both these design rules by creating a series of spin radical systems that have very efficient near-infrared emission (680–800 nm) from charge-transfer excitons. We show that these systems have substantial coupling to vibrational modes only below 250 cm -1 , frequencies that are too low to allow fast non-radiative decay. This enables non-radiative decay rates to be suppressed by nearly two orders of magnitude in comparison to π-conjugated molecules with similar bandgaps. Our results show that losses due to coupling to high-frequency modes need not be a fundamental property of these systems.

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

Charge separation in the photosystem II reaction center resolved by multispectral two-dimensional electronic spectroscopy

The photosystem II reaction center (PSII RC) performs the primary energy conversion steps of oxygenic photosynthesis. While the PSII RC has been studied extensively, the similar time scales of energy transfer and charge separation and the severely overlapping pigment transitions in the Qy region have led to multiple models of its charge separation mechanism and excitonic structure. Here, we combine two-dimensional electronic spectroscopy (2DES) with a continuum probe and two-dimensional electronic vibrational spectroscopy (2DEV) to study the cyt b559-D1D2 PSII RC at 77 K. This multispectral combination correlates the overlapping Qy excitons with distinct anion and pigment-specific Q x and mid-infrared transitions to resolve the charge separation mechanism and excitonic structure. Through extensive simultaneous analysis of the multispectral 2D data, we find that charge separation proceeds on multiple time scales from a delocalized excited state via a single pathway in which Pheo D1 is the primary electron acceptor, while Chl D1 and P D1 act in concert as the primary electron donor.

30 DIRECT ENERGY CONVERSION↗
NASA NTRS1987

Infrared emission from interstellar PAHs

The mid-IR absorption and Raman spectra of polycyclic aromatic hydrocarbons (PAHs) and the mechanisms determining them are reviewed, and the implications for observations of similar emission spectra in interstellar clouds are considered. Topics addressed include the relationship between PAHs and amorphous C, the vibrational spectroscopy of PAHs, the molecular emission process, molecular anharmonicity, and the vibrational quasi-continuum. Extensive graphs, diagrams, and sample spectra are provided, and the interstellar emission bands are attributed to PAHs with 20-30 C atoms on the basis of the observed 3.3/3.4-micron intensity ratios.

Allamandola, L. J.↗
NASA NTRS1999

The Thermal Emission Imaging System (THEMIS) Instrument for the Mars 2001 Orbiter

The primary objective of the Thermal Emission Imaging System (THEMIS) on the Mars Surveyor '01 Orbiter is to study the composition of the Martian surface at high spatial resolution. THEMIS will map the surface mineralogy using multi-spectral thermal infrared images in 8 spectral bands from 6.5 to 14.5 microns. In addition, a band centered at 15 microns will be used to map atmospheric temperatures and provide an important aid in separating the surface and atmospheric components. The entire planet will be mapped at 100 m resolution within the available data volume using a multi-spectral, rather than hyperspectral, imaging approach. THEMIS will also acquire 20 m resolution visible images in up to 5 spectral bands using a replica of the Mars 98 Orbiter (MARCI) and Lander (MARDI) cameras. Over 15,000 panchromatic (3,000 5-color), 20 x 20 km images will be acquired for morphology studies and landing site selection. The thermal-infrared spectral region contains the fundamental vibrational absorption bands of most minerals which provide diagnostic information on mineral composition. All geologic materials, including carbonates, hydrothermal silica, sulfates, phosphates, hydroxides, silicates, and oxides have strong absorptions in the 6.5-14.5 micron region. Silica and carbonates, which are key diagnostic minerals in thermal spring deposits, are readily identified using thermal-IR spectra. In addition, the ability to identify all minerals allows the presence of aqueous minerals to be interpreted in the proper geologic context. An extensive suite of studies over the past 35 years has demonstrated the utility of vibrational spectroscopy for the quantitative determination of mineralogy and petrology. The fundamental vibrations within different anion groups, such as C03, S04, P04, and SiO4, produce unique, well separated spectral bands that allow carbonates, sulfates, phosphates, silicates, oxides, and hydroxides to be readily identified. Additional stretching and bending modes involving major cations, such as Mg, Fe, Ca, and Na, allow Further mineral identification, such as the excellent discriminability of minerals within the silicate and carbonate groups.

Christensen, P. R.↗