Search NASA⌕ Search

SEARCH · Search NASA

Results for “MOLECULAR OSCILLATION”

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 NTRS1979

Predissociation of nitric oxide in the mesosphere and stratosphere

Absorption of solar photons by nitric oxide in the wavelength ranges 181.3-183.5 and 189.4-191.6 nm leads to predissociation of the molecule in the mesosphere and upper stratosphere. Molecular oxygen controls the penetration of the required solar irradiance via absorption in the Schumann-Runge bands, while attenuation due to ozone becomes significant in the upper stratosphere. The calculation of the nitric oxide dissociation rate is complicated by the need to include all rotational fine structure in both the NO and O2 cross sections. The dissociation rate computed here for the upper mesosphere is a factor of 3.6 less than that reported in past work when currently accepted values of the oscillator strengths and solar irradiance are used. In addition, improved molecular parameters describing the O2 cross section predict less attenuation of the dissociation rate with decreasing altitude than results previously available.

Frederick, J. E.↗
DOE OSTI2020

Polaritons and excitons: Hamiltonian design for enhanced coherence

The primary questions motivating this report are: Are there ways to increase coherence and delocalization of excitation among many molecules at moderate electronic coupling strength? Coherent delocalization of excitation in disordered molecular systems is studied using numerical calculations. The results are relevant to molecular excitons, polaritons, and make connections to classical phase oscillator synchronization. In particular, it is hypothesized that it is not only the magnitude of electronic coupling relative to the standard deviation of energetic disorder that decides the limits of coherence, but that the structure of the Hamiltonian—connections between sites (or molecules) made by electronic coupling—is a significant design parameter. Inspired by synchronization phenomena in analogous systems of phase oscillators, some properties of graphs that define the structure of different Hamiltonian matrices are explored. The report focuses on eigenvalues and ensemble density matrices of various structured, random matrices. Some reasons for the special delocalization properties and robustness of polaritons in the single-excitation subspace (the star graph) are discussed. The key result of this report is that, for some classes of Hamiltonian matrix structure, coherent delocalization is not easily defeated by energy disorder, even when the electronic coupling is small compared to disorder.

Science & Technology - Other Topics↗
NASA NTRS2006

NASA Laboratory Astrophysics Workshop 2006 Introductory Remarks

NASA Laboratory Astrophysics Workshop 2006, is the fourth in a series of workshops held at four year intervals, to assess the laboratory needs of NASA's astrophysics missions - past, current and future. Investigators who need laboratory data to interpret their observations from space missions, theorists and modelers, experimentalists who produce the data, and scientists who compile databases have an opportunity to exchange ideas and understand each other's needs and limitations. The multi-wavelength character of these workshops allows cross-fertilization of ideas, raises awareness in the scientific community of the rapid advances in other fields, and the challenges it faces in prioritizing its laboratory needs in a tight budget environment. Currently, we are in the golden age of Space Astronomy, with three of NASA s Great Observatories, Hubble Space Telescope (HST), Chandra X-Ray Observatory (CXO), and Spitzer Space Telescope (SST), in operation and providing astronomers and opportunity to perform synergistic observations. In addition, the Far Ultraviolet Spectroscopic Explorer (FUSE), XMM-Newton, HETE-2, Galaxy Evolution Explorer (GALEX), INTEGRAL and Wilkinson Microwave Anisotropy Probe (WMAP), are operating in an extended phase, while Swift and Suzaku are in their prime phase of operations. The wealth of data from these missions is stretching the Laboratory Astrophysics program to its limits. Missions in the future, which also need such data include the James Webb Space Telescope (JWST), Space Interferometry Mission (SIM), Constellation-X (Con-X), Herschel, and Planck. The interpretation of spectroscopic data from these missions requires knowledge of atomic and molecular parameters such as transition probabilities, f-values, oscillator strengths, excitation cross sections, collision strengths, which have either to be measured in the laboratory by simulating space plasma and interactions therein, or by theoretical calculations and modeling. Once the laboratory data are obtained, a key step to making them available to the observer is the creation and maintenance of critically compiled databases. Other areas of study, that are important for understanding planet formation, and for detection of molecules that are indicators of life, are also supported by the Laboratory Astrophysics program. Some examples are: studies of ices and dust grains in a space environment; nature and evolution of interstellar carbon-rich dust; and polycyclic aromatic hydrocarbons. In addition, the program provides an opportunity for the investigation of novel ideas, such as simulating radiative shock instabilities in plasmas, in order to understand jets observed in space. A snapshot of the currently funded program, mission needs, and relevance of laboratory data to interpreting observations, will be obtained at this workshop through invited and contributed talks and poster papers. These will form the basis for discussions in splinter groups. The Science Organization Committee will integrate the results of the discussions into a coherent White Paper, which will provide guidance to NASA in structuring the Laboratory Astrophysics program in subsequent years, and also to the scientific community in submitting research proposals to NASA for funding.

Hasan, Hashima↗
NASA NTRS2010

Oscillation of Angiogenesis and Vascular Dropout in Progressive Human Vascular Disease

When analyzed by VESsel GENeration Analysis (VESGEN) software, vascular patterns provide useful integrative read-outs of complex, interacting molecular signaling pathways. Using VESGEN, we recently discovered and published our innovative, surprising findings that angiogenesis oscillated with vascular dropout throughout progression of diabetic retinopathy, a blinding vascular disease. Our findings provide a potential paradigm shift in the current prevailing view on progression and treatment of this disease, and a new early-stage window of regenerative therapeutic opportunities. The findings also suggest that angiogenesis may oscillate with vascular disease in a homeostatic-like manner during early stages of other inflammatory progressive diseases such as cancer and coronary vascular disease.

Parsons-Wingerter, Patricia↗
DOE OSTI2024

Dynamic embedding of effective harmonic normal mode vibrations in all-atomistic energy gap fluctuations: Case study of light harvesting 2 complex

Environmental effects in excitation energy transfer have mostly been modeled by baths of harmonic oscillators, but to what extent such modeling provides a reliable description of actual interactions between molecular systems and environments remains an open issue. Here, we address this issue by investigating fluctuations in the excitation energies of the light harvesting 2 complex using a realistic all-atomistic simulation of the potential energy surface. Our analyses reveal that molecular motions exhibit significant anharmonic features, even for underdamped intramolecular vibrations. In particular, we find that the anharmonicity contributes to the broadening of spectral densities and substantial overlaps between neighboring peaks, which complicates the meaning of mode frequencies constituting a bath model. Thus, we develop a strategy to construct a minimally underdamped harmonic bath that has a clear connection to all-atomistic dynamics by utilizing actual normal modes of molecules but optimizing their frequencies such that the resulting bath model can best reproduce the all-atomistic simulation results. By subtracting the underdamped contribution from the entire fluctuations, we also show that identifying a residual spectral density representing all other contributions with overdamped behavior is possible. We find that this can be fitted well with a well-established analytic form of a spectral density function or, alternatively, modeled as explicit time dependent fluctuations with muti-exponential or power law type correlation functions. We provide an assessment and the implications of these possibilities. The approach presented here can also serve as a general strategy to construct a simplified bath model that can effectively represent the underlying all-atomistic bath dynamics.

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

A generalized class of strongly stable and dimension-free T-RPMD integrators

Here, recent work shows that strong stability and dimensionality freedom are essential for robust numerical integration of thermostatted ringpolymer molecular dynamics (T-RPMD) and path-integral molecular dynamics, without which standard integrators exhibit non-ergodicity and other pathologies [R. Korol et al., J. Chem. Phys. 151, 124103 (2019) and R. Korol et al., J. Chem. Phys. 152, 104102 (2020)]. In particular, the BCOCB scheme, obtained via Cayley modification of the standard BAOAB scheme, features a simple reparametrization of the free ring-polymer sub-step that confers strong stability and dimensionality freedom and has been shown to yield excellent numerical accuracy in condensed-phase systems with large time steps. Here, we introduce a broader class of T-RPMD numerical integrators that exhibit strong stability and dimensionality freedom, irrespective of the Ornstein–Uhlenbeck friction schedule. In addition to considering equilibrium accuracy and time step stability as in previous work, we evaluate the integrators on the basis of their rates of convergence to equilibrium and their efficiency at evaluating equilibrium expectation values. Within the generalized class, we find BCOCB to be superior with respect to accuracy and efficiency for various configuration-dependent observables, although other integrators within the generalized class perform better for velocity-dependent quantities. Extensive numerical evidence indicates that the stated performance guarantees hold for the strongly anharmonic case of liquid water. Both analytical and numerical results indicate that BCOCB excels over other known integrators in terms of accuracy, efficiency, and stability with respect to time step for practical applications.

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

Assessing entropy for catalytic processes at complex reactive interfaces

When chemical reactions are accelerated by a catalyst, entropy differences between reactants and their transient intermediates can be the driving force behind the promotion or inhibition of desired and parasitic chemical pathways. Understanding and controlling catalytic processes therefore requires both a fundamental and practicable understanding of entropy in addition to enthalpy. In unstructured media such as the vapor phase equilibrated with sparsely covered surfaces, entropy can be adequately accounted for by well-established approaches based on translational, rotational, and harmonic vibrational partition functions. However, these approximations become inadequate in more complex condensed phase environments, e.g., solid liquid interfaces of confined reaction spaces. In this chapter, we provide an overview of the state-of-art in the computational quantification of entropy and its known ramifications on catalysis. The fundamental roles of thermodynamics and kinetics in catalysis are covered in enough detail to appreciate and contextualize the computational methods employed to compute chemically accurate estimates of entropy. These methods are discussed in appropriate detail and range from the ubiquitous harmonic oscillator approximation where entropy unrelated to high frequency oscillations is typically underestimated, to enhanced free energy sampling with molecular dynamics where the desired accuracy must be weighed against the associated computational cost of obtaining it. The rising importance of machine learning and artificial intelligence in accelerating methodological progress in this field is touched upon, as well. Finally, applications, successes, and pitfalls of using these methods are provided to showcase past and present accomplishments while clarifying where improvements in both understanding and methodology are still needed.

Kollias, Loukas↗
DOE OSTI2025

VERITAS : A density-functional theory-based multiband kinetic model for understanding x-ray spectroscopy of dense plasmas

X-ray spectroscopy has long been a powerful diagnostic tool for hot, dilute plasmas, providing insights into plasma conditions by measuring line shifts and broadenings of atomic transitions. The technique critically depends on the accuracy of atomic physics models used to interpret spectroscopic measurements for inferring plasma properties such as free-electron density and temperature. Over the past decades, the atomic and plasma physics communities have developed robust atomic physics models to account for various processes in hot, dilute classical plasmas. While these models have been successful in that regime, their applicability becomes uncertain when interpreting x-ray spectroscopy experiments of above-solid-density plasmas. Given that finite-temperature density-functional theory (DFT) offers a more accurate description of dense plasma environments, we present the development of a DFT-based multi-band kinetic model, VERITAS, designed to improve the interpretation of x-ray spectroscopic measurements in high-density plasmas produced by laser-driven spherical implosions. This work details the VERITAS model and its application to both time-integrated and time-resolved x-ray spectra from implosion experiments on OMEGA. The advantages and limitations of the VERITAS model will also be discussed, along with potential directions for advancing x-ray spectroscopy of dense and superdense plasmas.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
NASA NTRS1969

Dipole properties of molecular hydrogen.

Molecular hydrogen electron scattering, optical refractivity and molecular anisotropy used to construct model dipole spectrum consistent with oscillator strength rules

Dalgarno, A.↗
NASA NTRS1976

Electronic transition CN laser

A 20 kW electric-discharge pumped CN laser oscillating on the A(2) Pi-X(2) Sigma molecular system is presented. Excitation is by a simple longitudinal discharge struck through HCN vapor. Twenty kW peak power is generated in a 150 nsec full-width half-maximum pulse. Two lasing bands were observed in the A-X system: the (0,1) and (0,2) bands near 1.42 and 2.0 microns respectively. Both P and Q branches are active in the two bands, with Q bands stronger. Peak laser energy is 3 mJ. Products of UV photolysis of HCN, electron impact excitation of HCN, and other possible excitation mechanisms and laser efficiency are discussed.

Quick, C. R., Jr.↗
NASA NTRS1983

High spectral resolution lidar to measure optical scattering properties of atmospheric aerosols. I - Theory and instrumentation

A high spectral resolution lidar technique to measure optical scattering properties of atmospheric aerosols is described. Light backscattered by the atmosphere from a narrowband optically pumped oscillator-amplifier dye laser is separated into its Doppler broadened molecular and elastically scattered aerosol components by a two-channel Fabry-Perot polyetalon interferometer. Aerosol optical properties, such as the backscatter ratio, optical depth, extinction cross section, scattering cross section, and the backscatter phase function, are derived from the two-channel measurements.

Shipley, S. T.↗
DOE OSTI2020

Rabi spectroscopy of the clock transition in thulium atoms in a one-dimensional optical lattice

The clock transition at a wavelength of 1.14 μm in thulium atoms in an optical lattice in the Lamb – Dick regime is studied. The capture of thulium atoms makes it possible to suppress completely both the transition broadening due to the first-order Doppler effect and the shift of the transition frequency caused by the recoil effect. The excitation spectra of sideband oscillation frequencies and Rabi oscillations of population between the clock transition levels upon resonance excitation are investigated. (paper)

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2023

Amplified spontaneous emission from europium-based molecular complexes coupled to photonic crystal cavities

Rare-earth ion-based materials bear many remarkable optical properties that render them highly appealing for lighting and quantum-related applications. However, their small oscillator strength and weak emission often pose limitations. Here, in this work, we synthesize and couple Eu(III)-based molecular complexes to nanobeam photonic crystals supporting air modes. A reasonable spatial overlap between the molecular complexes and cavity modes leads to an average spontaneous emission coupling efficiency of 0.19. Our pump power-dependent photoluminescence measurements evidence amplified spontaneous emission from the molecular complexes with an amplification threshold as low as 4.4 W/cm 2 , likely benefiting from the efficient coupling. These findings suggest that integrating rare-earth ion-based molecular complexes with photonic structures could be a viable approach for regulating their emission characteristics for particular applications.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Three-body Förster resonance of a new type in Rydberg atoms

The three-body Förster resonances 3 × nP{sub 3/2}(|M|) →nS{sub 1/2} + (n + 1)S{sub 1/2} + nP{sub 3/2}(|M*|), controlled by a constant electric field, were realised earlier by the authors in an ensemble of several cold Rydberg Rb atoms. One of the drawbacks of such resonances for potential application in three-qubit quantum gates is the proximity of the two-body Förster resonance 2 × nP{sub 3/2} → nS{sub 1/2} + (n + 1)S{sub 1/2}, as well as the possibility of their implementation only for states with values of the principal quantum numbers n ⩽38. A three-body resonance of a new type, 3 × nP{sub 3/2} → nS{sub 1/2} + (n + 1)S{sub 1/2} + nP{sub 1/2}, which can be realised for arbitrary n, is proposed and analysed. Its specific feature is also that the third atom transits into a state with a different total angular momentum J = 1/2, which has no Stark structure, so that the two-body resonance is completely absent. Numerical calculations showed that for not too strong interaction, it is possible to observe coherent three-body oscillations of the populations of collective states, which is of interest for developing new schemes of three-qubit quantum gates controlled by an electric field. (paper)

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2025

Probing Electronic Coherence between Core-Level Vacancies at Different Atomic Sites

The detailed understanding of electronic coherence in quantum systems requires measurements on the attosecond timescale. Attosecond x-ray pulses enable the study of electronic coherence in core-excited molecular systems. Here we report on the coherent motion of electrons in the 1,1-difluoroethylene ion following ionization of the K shell of the two nonequivalent carbon sites with a subfemtosecond x-ray pulse. Using the angular streaking technique to track the Auger-Meitner decay, we observe temporal modulations of the emission, indicating the electronic coherence of the core-excited ionic states, and extract a 6.5 ± 0.8 fs average lifetime of the core-level vacancies. A quantum-mechanical model is employed to interpret the measurement, and we find the observed temporal modulations are independent of charge density oscillations. This work opens a new regime of coherent electronic motion, beyond charge migration, where electronic coherence manifests in the nonlocal quantum correlation between atomic sites while charge density oscillation is absent. Our results broaden the landscape of electronic coherence in molecular systems. Published by the American Physical Society 2025

Wang, Jun (ORCID:000000031962895X)↗
DOE OSTI2022

Following excited-state chemical shifts in molecular ultrafast x-ray photoelectron spectroscopy

The conversion of photon energy into other energetic forms in molecules is accompanied by charge moving on ultrafast timescales. We directly observe the charge motion at a specific site in an electronically excited molecule using time-resolved x-ray photoelectron spectroscopy (TR-XPS). We extend the concept of static chemical shift from conventional XPS by the excited-state chemical shift (ESCS), which is connected to the charge in the framework of a potential model. This allows us to invert TR-XPS spectra to the dynamic charge at a specific atom. We demonstrate the power of TR-XPS by using sulphur 2p-core-electron-emission probing to study the UV-excited dynamics of 2-thiouracil. The method allows us to discover that a major part of the population relaxes to the molecular ground state within 220–250 fs. In addition, a 250-fs oscillation, visible in the kinetic energy of the TR-XPS, reveals a coherent exchange of population among electronic states.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1992

Laboratory astrophysics under the ultraviolet, visible, and gravitational astrophysics research program: Oscillator strengths for ultraviolet atomic transitions

The conditions within astrophysical environments can be derived from observational data on atomic and molecular lines. For instance, the density and temperature of the gas are obtained from relative populations among energy levels. Information on populations comes about only when the correspondence between line strength and abundance is well determined. The conversion from line strength to abundance involves knowledge of meanlives and oscillator strengths. For many ultraviolet atomic transitions, unfortunately, the necessary data are either relatively imprecise or not available. Because of the need for more and better atomic oscillator strengths, our program was initiated. Through beam-foil spectroscopy, meanlives of ultraviolet atomic transitions are studied. In this technique, a nearly isotopically pure ion beam of the desired element is accelerated. The beam passes through a thin carbon foil (2 mg/cu cm), where neutralization, ionization, and excitation take place. The dominant process depends on the energy of the beam. Upon exiting the foil, the decay of excited states is monitored via single-photon-counting techniques. The resulting decay curve yields a meanlife. The oscillator strength is easily obtained from the meanlife when no other decay channels are presented. When other channels are present, additional measurements or theoretical calculations are performed in order to extract an oscillator strength. During the past year, three atomic systems have been studied experimentally and/or theoretically; they are Ar, I, Cl I, and N II. The results for the first two are important for studies of interstellar space, while the work on N II bears on processes occurring in planetary atmospheres.

Federman, Steven R.↗