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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 649 records · Page 36
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Mode-Selective Vibrational Energy Transfer Dynamics in 1,3,5-Trinitroperhydro-1,3,5-triazine (RDX) Thin Films

The coupling of inter- and intramolecular vibrations plays a critical role in initiating chemistry during the shock-to-detonation transition in energetic materials. In this work, we report on the subpicosecond to subnanosecond vibrational energy transfer (VET) dynamics of the solid energetic material 1,3,5-trinitroperhydro-1,3,5-triazine (RDX) by using broadband, ultrafast infrared transient absorption spectroscopy. Experiments reveal VET occurring on three distinct time scales: subpicosecond, 5 ps, and 200 ps. The ultrafast appearance of signal at all probed modes in the mid-infrared suggests strong anharmonic coupling of all vibrations in the solid, whereas the long-lived evolution demonstrates that VET is incomplete, and thus thermal equilibrium is not attained, even on the 100 ps time scale. Density functional theory and classical molecular dynamics simulations provide valuable insights into the experimental observations, revealing compression-insensitive time scales for the initial VET dynamics of high-frequency vibrations and drastically extended relaxation times for low-frequency phonon modes under lattice compression. Mode selectivity of the longest dynamics suggests coupling of the N–N and axial NO2 stretching modes with the long-lived, excited phonon bath.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1985

Molecular spectroscopy from the Kuiper Airborne Observatory

Interstellar and circumstellar molecules are investigated through medium-resolution infrared spectrosocpy of the vibration-rotation and pure rotational transitions. A primary goal was the construction and improvement of instrumentation for the near and middle infrared regions, wavelengths between 2 and 10 microns. The main instrument was a cooled grating spectrometer with an interchangeable detector focal plane which could be used on the Kuiper Airborne Observatory (KAO) for airborne observations, and also at ground-based facilities. Interstellar shock waves were investigated by H2 emission from the Orion Nebula, W51, and the proto-planetary nebulae CRL 2688 and CRL 618. The observations determined the physical conditions in shocked molecular gas near these objects. From these it was possible to characterize the energetic history of mass loss from both pre- and post-main sequence stars in the regions.

Beckwith, S.↗
NASA NTRS1989

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.↗
DOE OSTI2023

Dispersion-Engineered Deep Sub-Wavelength Plasmonic Metasurfaces for Broadband Seira Applications

Surface enhanced infrared absorption (SEIRA) spectroscopy is a powerful tool in which plasmonically enhanced electromagnetic fields provide high-sensitivity molecular detection. Most SEIRA platforms operate at a single resonant frequency, which must be tuned to match that of the target molecule, and commonly rely on time-consuming lithographic techniques. This study presents a high-throughput and cost-effective plasmonic metasurface for broadband, tunable, and strong infrared signal enhancement. The platform is built upon the principle of dispersion-engineered plasmonic Fabry–Pérot (FP) nanocavity arrays. It offers 1) tight squeezing of infrared (IR) photons into deep sub-wavelength nano-volumes and 2) spectrally tunable near-field enhancements of up to ≈10 6 , two to three orders of magnitude higher than most optical metasurface systems. By coupling multilayer nano-thin film deposition and nanoskiving fabrication techniques, the dispersive FP metasurfaces can be rapidly and reproducibly constructed in a scalable and lithography-free manner. Using IR spectroscopy, the selective and sensitive label-free detection of a molecular monolayer is achieved at a range of frequencies. An enhancement factor of nearly 10 5 is measured at the carbonyl (C = O) vibrational marker band of the molecule. The confluence of high field enhancement, broadband plasmonic response, and facile fabrication makes this metasurface a promising platform for SEIRA spectroscopy.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Cosolvent-tuned interactions in ionic liquids: A vibrational and quantum-chemical study of ethylene glycol ratio effects

Ionic liquids (ILs) are attractive media for CO 2 capture but remain limited by viscosity and cost. Blending ILs with ethylene glycol (EG) is a practical route to mitigate these constraints, yet the molecular origins of cosolvent effects and their dependence on composition are not well resolved. We combine Fourier-transform infrared (FT-IR) spectroscopy with quantum-chemical (DFT) analysis to elucidate how the IL:EG molar ratio modulates intermolecular interactions and electronic structure. Computed vibrational frequencies enable mode assignment and deconvolution of overlapping bands, revealing systematic, ratio-dependent shifts and broadenings in (i) EG O–H stretching, (ii) cation and EG C–H stretchings (imidazolium C2–H, C4–H, C5–H, methyl and ethyl groups, -CH2 of EG), (iii) anion signature modes (e.g., CN motifs), and (iv) EG C–O and C–C stretchings, consistent with the redistribution of hydrogen-bonding networks. Molecular electrostatic potential (MESP) maps quantify attenuation of extreme potential regions with increasing EG, indicating progressive screening of cation–anion electrostatic interactions. Quantum Theory of Atoms in Molecules (QTAIM) identifies emergent bond critical points between EG and the IL ions, while Reduced Density Gradient–Noncovalent Interaction (RDG–NCI) analysis differentiates strong directional hydrogen bonds from dispersive contacts across compositions. Together, these results show that EG fraction controls a switch from predominantly ion–ion to mixed ion–EG coordination, altering local polarity and polarizability that underlie the observed FT-IR trends. The framework provides composition–structure–spectrum relationships that can guide rational selection of IL:EG ratios to balance favorable molecular interactions with practical performance targets in scalable CO 2 capture systems.

DAC↗
DOE OSTI2024

Operando Investigation of the Molecular Origins of Dipole Switching in P(VDF‐TrFE‐CFE) Terpolymer for Large Adiabatic Temperature Change

Abstract Relaxor ferroelectric polymers exhibiting a giant electrocaloric effect (ECE) can potentially be used to create next‐generation solid‐state coolers. Under an electric field, poly(vinylidene fluoride‐trifluoroethylene‐chlorofluoroethylene) terpolymer goes through a large dipolar entropy change producing a high adiabatic temperature change (Δ T ECE ). This work resolves the molecular origins of the large entropy change behind the electric field‐induced dipole switching. A Fourier transform infrared spectroscopy equipped with a high voltage source is used to operandoly observe the characteristic molecular vibrational modes. A short‐range trans (T) conformation of the CF 2 ‐CH 2 dyads interrupted by a gauche (G) conformation, e.g., TTTG in the terpolymer chain, undergoes a dynamic transformation that leads to a corresponding Δ T ECE whenever an electric field is applied. The molecular dynamics simulation also proves that the energy barrier that the transformation from TTTGs into a long T sequence overcomes is smaller than that for all other conformations. A mixed solvent system is used to obtain T3G‐enriched terpolymer films exhibiting a 4.02 K Δ T ECE at 60 MV m −1 and these films are employed to manufacture a 2‐layer‐cascaded cooling device that achieves a 6.7 K temperature lift, the highest reported value for a 2‐layer cascaded device made of fluoropolymers.

Zhu, Yuan↗
DOE OSTI2022

Machine Learning for Optical Scanning Probe Nanoscopy

Abstract The ability to perform nanometer‐scale optical imaging and spectroscopy is key to deciphering the low‐energy effects in quantum materials, as well as vibrational fingerprints in planetary and extraterrestrial particles, catalytic substances, and aqueous biological samples. These tasks can be accomplished by the scattering‐type scanning near‐field optical microscopy (s‐SNOM) technique that has recently spread to many research fields and enabled notable discoveries. Herein, it is shown that the s‐SNOM, together with scanning probe research in general, can benefit in many ways from artificial‐intelligence (AI) and machine‐learning (ML) algorithms. Augmented with AI‐ and ML‐enhanced data acquisition and analysis, scanning probe optical nanoscopy is poised to become more efficient, accurate, and intelligent.

Chen, Xinzhong↗
DOE OSTI2021

Low-frequency Raman signature of Ag-intercalated few-layer MoS 2

Density functional theory based calculations and experimental analysis on a limited number of real samples are performed to study how the presence of silver intercalated in the van der Waals gap of few-layer MoS 2 affects the low-frequency Raman active modes of this material. Silver is found to predominantly affect the breathing-like and shear-like vibrational modes of MoS 2 . These modes correspond to quasi-rigid movements of each individual layer with a restoring force (and, in turn, frequency) that is determined by modulations in the weak interlayer interactions. Noticeable red-shifts with increasing Ag concentration are found for all low-frequency modes. This finding indicates the potential for low-frequency vibrations as useful gauges for practical determination of silver concentration using low-frequency Raman spectroscopy. Finally, this work also describes a semi-classical linear chain model that allows to extrapolate results to a large number of layers. Further, first-principles calculations show how Raman spectroscopy can be used to characterize the quality of the two-dimensional interface between MoS 2 and a silver substrate.

36 MATERIALS SCIENCE↗
NASA NTRS1996

The v4 Band of FNO2

We report the first high resolution infrared spectra of nitryl fluoride, FNO(sub 2). The intense V(sub 4) band, associated with the NO(sub 2) antisymmetric streteching vibration, has been observed.

high resolution spectroscopy infrared b-type trans↗
NASA NTRS1982

Effect of hydrogen bonding on the vibrational dephasing time in glycerol

The vibrational dephasing of the methyl CH2 symmetric stretch mode in glycerol was directly measured over an extended temperature range using picosecond coherent Raman pump and probe spectroscopy. The dephasing time was found to increase dramatically as the temperature of the supercooled liquid was lowered. This observation is attributed to the increased hydrogen bonding with decreasing temperature which hinders the dephasing of the CH2 vibration by reducing molecular motions.

Dorsinville, R.↗
DOE OSTI2024

Distinct vibrational motions promote disparate excited-state decay pathways in cofacial perylenediimide dimers

A complex interplay of structural, electronic, and vibrational degrees of freedom underpins the fate of molecular excited states. Organic assemblies exhibit a myriad of excited-state decay processes, such as symmetry-breaking charge separation (SB-CS), excimer (EX) formation, singlet fission, and energy transfer. Recent studies of cofacial and slip-stacked perylene-3,4:9,10-bis(dicarboximide) (PDI) multimers demonstrate that slight variations in core substituents and H- or J-type aggregation can determine whether the system follows an SB-CS pathway or an EX one. However, questions regarding the relative importance of structural properties and molecular vibrations in driving the excited-state dynamics remain. Here, we use a combination of two-dimensional electronic spectroscopy, femtosecond stimulated Raman spectroscopy, and quantum chemistry computations to compare the photophysics of two PDI dimers. The dimer with 1,7-bis(pyrrolidin-1′-yl) substituents (5PDI2) undergoes ultrafast SB-CS from a photoexcited mixed state, while the dimer with bis-1,7-(3′,5′-di-t-butylphenoxy) substituents (PPDI2) rapidly forms an EX state. Examination of their quantum beating features reveals that SB-CS in 5PDI2 is driven by the collective vibronic coupling of two or more excited-state vibrations. In contrast, we observe signatures of low-frequency vibrational coherence transfer during EX formation by PPDI2, which aligns with several previous studies. We conclude that key electronic and structural differences between 5PDI2 and PPDI2 determine their markedly different photophysics.

Chemistry↗
DOE OSTI2020

Observation of a Symmetry-Forbidden Excited Quadrupole-Bound State

In this paper, we report the observation of a symmetry-forbidden excited quadrupole-bound state (QBS) in the tetracyanobenzene anion (TCNB - ) using both photoelectron and photodetachment spectroscopies of cryogenically-cooled anions. The electron affinity of TCNB is accurately measured as 2.4695 eV. Photodetachment spectroscopy of TCNB - reveals selected symmetry-allowed vibronic transitions to the QBS, but the ground vibrational state was not observed because the transition from the ground state of TCNB - (A u symmetry) to the QBS (Ag symmetry) is triply-forbidden by the electric and magnetic dipoles, and the electric quadrupole. The binding energy of the QBS is found to be 0.2206 eV, which is unusually large due to strong correlation and polarization effects. A centrifugal barrier is observed for near-threshold autodetachment, as well as relaxations from the QBS vibronic levels to the ground and a valence excited state of TCNB - . The current study shows a rare example where symmetry selection rules, rather than the Franck-Condon principle, govern vibronic transitions to a non-valence state in an anion.

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

Electronic and vibrational properties of bulk Cr 2 Ge 2 Te 6 from first-principles calculations

Here we use density functional theory based ab initio calculations to investigate the structural, vibrational, magnetic, and electronic properties of the layered ferromagnet Cr 2 Ge 2 Te 6 (CGT) that has attracted attention for potential spintronic applications. We optimize the structure for a fixed c/a ratio. Our results are in excellent agreement with experimental data on structure, phonons, and electronic properties. The use of van der Waals interactions and relativistic spin-orbit coupling yields accurate lattice constants and interlayer distances. Simultaneously, the adopted theoretical methods lead to a rigorous description of the vibrational normal modes, as well as the valence bands, that are in excellent agreement with Raman spectroscopy and angle-resolved photoemission spectroscopy spectra, respectively. The magnetic moment is slightly overestimated, and the magnetic anisotropy has the correct sign but is greater in magnitude than that in experiment. We find that inclusion of the on-site Coulomb repulsion on Cr−3d orbitals worsens agreement with experiment, in contrast to previous studies. Our results provide a path toward ab initio analysis of magnetic heterostructures based on CGT.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Spin-phonon interaction and short-range order in Mn 3 Si 2 Te 6

The vibrational properties of ferrimagnetic Mn 3 Si 2 Te 6 single crystals are investigated using Raman spectroscopy and density functional theory calculations. Eighteen Raman-active modes are identified, 14 of which are assigned according to the trigonal symmetry. Four additional peaks, obeying the A 1g selection rules, are attributed to the overtones. The unconventional temperature evolution of the A$^{5}_{1g}$ mode self-energy suggests a competition between different short-range magnetic correlations that significantly impact the spin-phonon interaction in Mn 3 Si 2 Te 6 . This research provides comprehensive insight into the lattice properties, studies their temperature dependence, and shows arguments for the existence of competing short-range magnetic phases in Mn 3 Si 2 Te 6 .

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Applying Mechanistic Co-Design Towards Room-Temperature Organic, Optical, and Multiple-Center Molecular Qubits

The next generation of qubits, the building blocks of quantum technologies, are designed using molecules. Molecular qubits have natural advantages over solid-state equivalents in biological and chemical sensing. Chemistry allows the properties of molecular qubits to be fine-tuned, such as the ability of multiple qubits to work together using qubit-qubit coupling. Molecules and structures containing multiple qubits, made from both inorganic and organic elements, are developed in this work to bring quantum technologies closer to room-temperature operation. The goal is achieved by understanding how the core of the qubit, known as spin, interacts with the vibrating parts of the molecule, other spins, and the surrounding environment. A combined approach involving theory, spectroscopy, and synthesis is used to achieve the design goal.

36 MATERIALS SCIENCE↗
NASA NTRS1979

Optical constants of alcohols in the infrared

The spectral reflectances at near-normal incidence for methanol, ethanol, 1-propanol, 1-butanol, and 1-pentanol are reported for the spectral range 6700-350 kaysers. The real and imaginary parts of the complex index of refraction of these liquids are obtained in the range 4000-400 kaysers by use of Kramers-Kronig phase-shift analysis. For all of the alcohols studied, the strength for the OH-stretch bands is directly proportional to the number of OH groups per unit volume; similar relations are established for CH- and CO-stretch bands. Absorption cross sections for stretch vibrations of the three groups are considered, and the role of characteristic group intensities in intensity spectroscopy is discussed.

Sethna, P. P.↗
DOE OSTI2020

Nonlinear spectroscopy in the condensed phase: The role of Duschinsky rotations and third order cumulant contributions

First-principles modeling of nonlinear optical spectra in the condensed phase is highly challenging because both environment and vibronic interactions can play a large role in determining spectral shapes and excited state dynamics. In this work, we compute two dimensional electronic spectroscopy (2DES) signals based on a cumulant expansion of the energy gap fluctuation operator, with specific focus on analyzing mode mixing effects introduced by the Duschinsky rotation and the role of the third order term in the cumulant expansion for both model and realistic condensed phase systems. We show that for a harmonic model system, the third order cumulant correction captures effects introduced by a mismatch in curvatures of ground and excited state potential energy surfaces, as well as effects of mode mixing. We also demonstrate that 2DES signals can be accurately reconstructed from purely classical correlation functions using quantum correction factors. We then compute nonlinear optical spectra for the Nile red and methylene blue chromophores in solution, assessing the third order cumulant contribution for realistic systems. We show that the third order cumulant correction is strongly dependent on the treatment of the solvent environment, revealing the interplay between environmental polarization and the electronic-vibrational coupling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗