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Results for “Vibrational states”

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 523 records · Page 29
All sourcesNASA NTRSDOE OSTI
NASA NTRS1990

The heat of formation of CN radicals and radiative lifetimes of the A 1 Sigma - state of C2N2

Radiative lifetimes have been measured for the stable vibrational levels of the A 1 sigma - electronic state of C2N2. They range from 1.3 microsec for the 4(sub 0)(sup 1) level to 0.66 microsec for the 1(sub 0)(sup 1) 4(sub 0)(sup 1) level and in general decrease with increasing vibrational excitation. Self-quenching rate constants range from gas kinetic to ten times that. Foreign gas quenching rates are slower. Observation of emission from the 1(sub 0)(sup 1) 4(sub 0)(sup 1) level sets a lower limit for the heat of formation of CN of 439.11 kJ/mol.

Barts, Samuel A.↗
DOE OSTI2024

Nonequivalent Atomic Vibrations at Interfaces in a Polar Superlattice

In heterostructures made from polar materials, e.g., AlN–GaN–AlN, the nonequivalence of the two interfaces is long recognized as a critical aspect of their electronic properties; in that, they host different 2D carrier gases. Interfaces play an important role in the vibrational properties of materials, where interface states enhance thermal conductivity and can generate unique infrared-optical activity. The nonequivalence of the corresponding interface atomic vibrations, however, is not investigated so far due to a lack of experimental techniques with both high spatial and high spectral resolution. Herein, the nonequivalence of AlN–(Al 0.65 Ga 0.35 )N and (Al 0.65 Ga 0.35 )N–AlN interface vibrations is experimentally demonstrated using monochromated electron energy-loss spectroscopy in the scanning transmission electron microscope (STEM-EELS) and density-functional-theory (DFT) calculations are employed to gain insights in the physical origins of observations. It is demonstrated that STEM-EELS possesses sensitivity to the displacement vector of the vibrational modes as well as the frequency, which is as critical to understanding vibrations as polarization in optical spectroscopies. The combination enables direct mapping of the nonequivalent interface phonons between materials with different phonon polarizations. Furthermore, the results demonstrate the capacity to carefully assess the vibrational properties of complex heterostructures where interface states dominate the functional properties.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Vibrational control of the reaction pathway in the H + CHD 3 → H 2 + CD 3 reaction

An accurate full-dimensional quantum state-to-state simulation of the six-atom title reaction based on first-principles theory is reported. Counterintuitive effects are found: Increasing the energy in the reactant’s CD 3 umbrella vibration reduces the energy in the corresponding product vibration. An in-depth analysis reveals the crucial role of the effective dynamical transition state: Its geometry is controlled by the vibrational states of the reactants and subsequently controls the quantum state distribution of the products. This finding enables generalizing the concept of transition state control of chemical reactions to the quantum state–specific level.

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

The interplay of excitonic delocalization and vibrational localization in optical lineshapes: A variational polaron approach

The dynamics of molecular excitonic systems are complicated by a competition between electronic coupling (which drives delocalization) and vibrational-electronic (vibronic) interactions (which tend to encourage electronic localization). A particular challenge of molecular systems is that they typically possess a large number of independent vibrations, with frequencies often spanning the entire spectrum of relevant electronic energy gaps. Recent spectroscopic observations and numerical simulations on a water-soluble chlorophyll-binding protein (WSCP) reveal a transition between two regimes of vibronic behavior, a Redfield-like regime in which low-frequency vibrations respond to a delocalized excitonic state, and a Förster-like regime where high-frequency vibrations act as incoherent excitations on individual pigments. Although numerical simulations can reproduce these effects, there is a need for a simple, systematic theory that accurately describes the smooth transition between these two regimes in experimental spectra. Here we address this challenge by generalizing the variational polaron transform approach of [Bloemsma et al., Chem. Phys. 481, 250 (2016)] to include arbitrary bath densities for systems with or without symmetry. We benchmark this theory against both numerical matrix-diagonalization methods and experimental 77 K fluorescence spectra for two WSCP variants, obtaining quite satisfactory agreement in both cases. Here, we apply this theory to offer an explanation for the large loss in apparent electronic coupling in the WSCP Q57K mutant and to examine the likely impact of the interplay between excitonic delocalization and vibrational localization on vibrational sideband shapes and apparent coupling strengths in high-resolution optical spectra for chlorophyll-protein complexes such as WSCP.

14 SOLAR ENERGY↗
NASA NTRS1971

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

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

Shemansky, D. E.↗
DOE OSTI2026

Deciphering the excited-state landscape of Cr(iii) tris(diimines) using [Cr(phen) 3 ] 3+

Earth-abundant Cr(III) polypyridines chromophores feature long-lived doublet ligand-field excited states. The thermally equilibrated 2 T 1 / 2 E ligand-field excited state manifold produces broad, structured UV-Vis-NIR absorption bands. Although ubiquitous across pseudo-octahedral Cr(III) diimine complexes, the dynamics and individual electronic transitions underlying these spectra have remained elusive. Here, we combine time-resolved spectroscopy and multiconfigurational calculations to assign ground- and excited-state absorption spectra of Cr(III) tris(1,10-phenanthroline), [Cr(phen) 3 ] 3+ , as a prototypical example for this class of complexes. Excited-state kinetics reveal a rapid biexponential decay of the initially prepared intraligand/ligand-to-metal charge transfer [ 4 ( 1 IL)/ 4 LMCT] excited state into the lowest 2 T 1 / 2 E state within 10 picoseconds, assigned to intersystem crossing and vibrational relaxation. Calculations identify broad excited-state absorption features associated with metal-centered ligand-field states ( 2 MC) mixed with intraligand ( 2 IL) transitions within the doublet manifold. These results provide detailed spectral assignments and highlight the need to include multiconfigurational ligand-based orbitals when modeling the spectral properties of Cr(III) coordination complexes.

Barth, Alexandra T. [North Carolina State Universi↗
DOE OSTI2022

Scattering-type scanning near-field optical microscopy with Akiyama piezo-probes

Recent developments of the scattering-type scanning near-field optical microscope at cryogenic temperatures (cryogenic s-SNOM or cryo-SNOM) have led to many breakthroughs in the studies of low energy excitations in quantum materials. However, the simultaneous demands on vibration isolation, low base temperature, precise nano-positioning, and optical access make the construction of a cryo-SNOM a daunting task. Adding to the overhead space required for a cryo-SNOM is the atomic force microscopy control, which predominantly utilizes a laser-based detection scheme for determining the cantilever tapping motion. In this work, we provide an alternative and straightforward route to performing s-SNOM using metal-coated Akiyama probes, where the cantilever tapping motion is detected through a piezoelectric signal. We show that the Akiyama-based cryo-SNOM attains high spatial resolution, good near-field contrast, and is able to perform imaging with a significantly more compact system compared to other cryo-SNOM implementations. Our results firmly establish the potential of s-SNOM based on self-sensing piezo-probes, which can easily accommodate far-infrared wavelengths and high magnetic fields in the future.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
NASA NTRS1983

Theoretical study of the AlO blue-green (B2Sigma + - X2Sigma +) band system

Two independent, extensive theoretical calculations are reported for the relative band strengths of the AlO (B2Sigma + - X2Sigma +) blue-green system and for the radiative lifetimes of the lowest few vibrational levels of the B2Sigma(+) state. The theoretical lifetimes, which include a small (less than -.5 percent) contribution from bound-bound transitions into the A2Pi state, are in excellent agreement with laser fluorescence studies. The theoretical lifetimes increase monotonically and very slowly with increasing vibrational quantum number. The relative band strengths for the blue-green system derived from the two theoretical calculations are in excellent agreement, but differ systematically from the relative band strengths of Linton and Nicholls (1969). The present results suggest that their self-absorption corrections are not large enough, resulting in relative intensities that are too large, especially for the weak bands with r centroids less than 1.5 A.

Partridge, H.↗
DOE OSTI2025

Strong, Yet Split Hydrogen Bonding with Ice Rules in Delafossite (H/D)RhO 2

Despite remaining enigmatic, strong hydrogen bonding provides an advanced design handle for tailoring the properties of functional materials. Here, in this study, 3 R –(H/D)RhO 2 delafossites (prepared by ion exchange of Na + from NaRhO 2 ) contain H/D in linear coordination with O, linking Rh III O 2 layers. Bragg and real-space X-ray and neutron scattering analysis, vibrational and solid-state NMR spectroscopy, and density functional theory (DFT)–based electronic structure calculations have been employed to understand the nature of the hydrogen bonding. Despite short distances between H/D and the two O to which they are bonded, a clear double-minimum corresponding to a shorter and longer (H/D)–O distance is established. The triangular lattices formed by H/D appear to display ice-like disorder, corroborated by low-temperature heat capacity measurements.

NMR spectroscopy↗
DOE OSTI2025

Delocalized Excitation Transfer in Open Quantum Systems with Long-Range Interactions

The interplay between coherence and system-environment interactions is at the basis of a wide range of phenomena, from quantum information processing to charge and energy transfer in molecular systems, biomolecules, and photochemical materials. In this work, we use a Frenkel exciton model with long-range interacting qubits coupled to a damped collective bosonic mode to investigate vibrationally assisted transfer processes in donor-acceptor systems featuring internal substructures analogous to light-harvesting complexes. We find that certain delocalized excitonic states maximize the transfer rate and that the entanglement is preserved during the dissipative transfer over a wide range of parameters. We investigate the reduction in transfer caused by static disorder, white noise, and finite temperature and study how transfer efficiency scales as a function of the number of dimerized monomers and the component number of each monomer, finding which excitonic states lead to optimal transfer. Finally, we provide a realistic experimental setting to realize this model in analog trapped-ion quantum simulators. Analog quantum simulation of systems comprising many and increasingly complex monomers could offer valuable insights into the design of light-harvesting materials, particularly in the nonperturbative intermediate parameter regime examined in this study, where classical simulation methods are resource intensive.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2024

Coherent Transfer of Lattice Entropy via Extreme Nonlinear Phononics in Metal Halide Perovskites

Entropy transfer in metal halide perovskites, characterized by significant lattice anharmonicity and low stiffness, underlies the remarkable properties observed in their optoelectronic applications, ranging from solar cells to lasers. The conventional view of this transfer involves stochastic processes occurring within a thermal bath of phonons, where the lattice arrangement and energy flow from higher- to lower-frequency modes. Here, we unveil a comprehensive chronological sequence detailing a conceptually distinct coherent transfer of entropy in a prototypical perovskite CH 3 NH 3 Pbl 3 . The terahertz periodic modulation imposes vibrational coherence into electronic states, leading to the emergence of mixed (vibronic) quantum beat between approximately 3 and 0.3 THz. We highlight a well-structured bidirectional time-frequency transfer of these diverse phonon modes, each developing at different times and transitioning from high to low frequencies from 3 to 0.3 THz, before reversing direction and ascending to around 0.8 THz. First-principles molecular dynamics simulations disentangle a complex web of coherent-phononic coupling pathways and identify the salient roles of the initial modes in shaping entropy evolution at later stages. Capitalizing on coherent entropy transfer and dynamic anharmonicity presents a compelling opportunity to exceed the fundamental thermodynamic (Shockley-Queisser) limit of photoconversion efficiency and to pioneer novel optoelectronic functionalities. Published by the American Physical Society 2024

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Angle-resolved polarized Raman spectroscopy study of phosphorene nanoribbons

We present a systematic angle-resolved polarized Raman spectroscopy (ARPRS) study of black phosphorus (BP) nanostructures formed via electrochemical sodium- and lithium-ion intercalation. Sodium intercalation leads to bundles of densely packed, highly uniform phosphorene nanoribbons (PNRs) separated by parallel amorphous channels, whereas lithium intercalation results in shorter, irregular nanoribbon-like segments with lower aspect ratios. In both cases, six additional Raman peaks (P1–P6) appear alongside the three primary Raman-active modes of BP (A$^{1}_{g}$, B 2g , and A$^{2}_{g}$). These peaks are attributed to the amorphous regions, as confirmed by their isotropic angular dependence in ARPRS measurements. The three BP modes show pronounced angular variations that differ significantly between the two intercalated samples. In sodium-intercalated BP, A$^{1}_{g}$ and A$^{2}_{g}$ modes retain a dumbbell-like angular dependence under parallel polarization with enhanced anisotropy and reduced symmetry under crossed polarization. At the same time, the B 2g mode transitions from four-lobed (cloverleaf) polar plot to a butterfly-like one. In contrast, lithium-intercalated BP exhibits weaker anisotropy and less distinct angular polar plots for all three modes. These differences reflect the sensitivity of phonon behavior to underlying nanostructure morphology. The vibrational frequencies density of states (FDOS) calculations attribute the B 2g mode transformation to phonon band folding and mode mixing in PNRs. This study demonstrates the power of ARPRS in probing phonon-structure relationships and highlights the influence of edge geometry and quantum confinement on phonon dispersion in PNRs.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
NASA NTRS1966

Friction brake cushions acceleration and vibration loads

Friction brake cushions an object in a vehicle from axially applied vibration and steady-state acceleration forces. The brake incorporates a doubly tapered piston that applies a controlled radial force to friction brake segments bearing against the walls of a cylinder.

Fraser, G. F.↗
NASA NTRS1974

Study of vibrations produced by a vibrating beam used for vibrating concretes

For compacting concretes in building, vibrating beams are used. The vibrations are generated by inertial vibrators, and the beam is normally displaced by the operator by means of a handle that is elastically fastened to the beam by means of rubber pads. Considered are vibrations transmitted to the operator, taking into account the beam's shock vibration motions. The steady state motion of a dynamic beam pattern is studied, and results of experimental tests with existing equipment are presented.

Silas, C.↗
NASA NTRS1974

On the theory of H2 rotational excitation

A number of mechanisms for exciting higher-J states in the ground vibrational level are considered. Attention is given to collisions with H atoms and electrons. Other mechanisms involve a cascading down from upper vibrational levels, following absorption and reemission of photons in the Lyman and Werner bands, or a cascading down from upper vibrational levels, following formation of hydrogen molecules in excited vibrational and rotational levels. Theoretical population densities of rotational levels are shown in a graph.

Spitzer, L., Jr.↗
NASA NTRS1981

Peculiarities of spectra of induced emission of polymethine dye solutions at low temperatures

Results from studying the induced emission spectra with monochromatic excitation (superluminescent regime) within a temperature range of 300 K - 5.2 K are presented. The significant feature of such operations is the appearance of quasi-lines whose minimum width is realized at 4.2 K. The frequency distribution of the quasi-lines unambiguously characterizes the dye investigated. When interpreting these results, the idea of an inhomogeneous broadening of the polymethine dye spectra in the solution being studied experimentally was used for the first time. The quasi-lines observed are interpreted as a manifestation of the electron vibration structure of singlet states of a complex molecule.

Melishchuk, M. V.↗