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At least 253 records · Page 14

Coherent laser excitation of Ba-137 and Ba-138

Computations are carried out for the 1S(6s2)-1P(6s,6p) coherent laser excitation of Ba-137 and Ba-138 in a magnetic field. Results are presented for both the steady-state and time-dependent excited-state populations of the Zeeman-split magnetic sublevels. The quantum-statistical Liouville-equation approach (for the reduced density matrix) is compared to the rate-equations approach. Significant differences are found between these, due to the interference between strongly overlapping lines (especially for Ba-137). The time-evolution profiles indicate that the Ba-137 transient time is much longer than that of Ba-138.

Lam, Kai-Shue↗

Plume characteristics of an arcjet thruster

An experimental investigation is conducted of the plume of a 1.5 kW hydrogen-fueled arcjet thruster. The velocity and translational temperature are measured by laser induced fluorescence of excited-state atomic hydrogen at a variety of locations and operating conditions. The peak velocity and temperature at the center of the exit plane of 14.7 km/s and 5000 K lead to a Mach number of 1.9. Evidence is presented which demonstrates the extent to which viscous forces dominate the flow, such as the exit plane Reynolds number of 18. Data taken in the plume suggest a transition from supersonic to subsonic flow via viscous dissipation. In addition, the results suggest that high tank pressures (0.4 to 1.5 Torr) limit the ability to simulate space environments for different portions of the plume.

Liebeskind, John G.↗

Investigation of infra-red and nonequilibrium air radiation

This report describes progress on the first year of a research program on the infrared radiation of air plasmas conducted in the High Temperature Gasdynamics Laboratory at Stanford University. This program is intended to investigate the masking of infrared signatures by the air plasma formed behind the bow shock of high velocity missiles. To this date, the radiative emission of air plasmas in the infrared has been the object of few experimental investigations, and although several infrared systems are already modeled in radiation codes such as NEQAIR, measurements are required to validate numerical predictions and indicate whether all transitions of importance are accounted for. The present program is motivated by the fact that 9 excited states (A, B, C, D, B', F, H, and H') of NO radiate in the infrared, especially between 1 and 1.5 microns where at least 9 transitions involving can be observed. Because these IR transitions are relatively well separated from each other, excited NO states concentrations can be easily measured, thus providing essential information on excited-state chemistry for use in optical diagnostics or in electronic excitation model validation. Developing accurate collisional-radiative models for these excited NO states is of importance as the UV-VUV transitions of NO (beta, gamma, epsilon, beta prime, gamma prime) produce a major, if not dominant, fraction of the radiation emitted by air plasmas. During the first year of the program, research has focused on the spectral range 1.0 to 1.5 microns, as detailed in Section 2 of this report. The measurements, conducted in a 50 kW radio-frequency inductively coupled plasma torch operating on air at atmospheric pressure, extend previous shock tube investigations by Wray to a wider spectral range (1.0 to 1.5 microns vs 0.9 to 1.2 microns) and higher temperatures (7600 K in the plasma torch versus 6700 K in the shock-tube). These higher temperatures in the present experiment have made it possible to observe high-lying excited NO states that were previously undetectable. These measurements are currently being extended up to 5 microns, with particular attention paid to the rovibronic bands of ground state NO, molecular continua, CO transitions, and other systems of importance. Publications and presentations resulting from or related to this work are cited in Section 3, and Section 4 lists the personnel who contributed to this report.

Kruger, Charles H.↗

Photodissociation of cyanoacetylene: Application to the atmospheric chemistry of Titan

The quantum yield and reaction threshold for the photochemical dissociation of cyanoacetylene into a hydrogen atom and the cyanoethynyl radical have been determined. The quantum yield at 185 nm is approximately 0.09. The threshold is approximately 240 nm. Combination of this data with literature values shows that production of excited-state cyanoacetylene is the major primary process resulting from irradiation between 185 and 254 nm. Also determined are the relative rate constants for the abstraction of a hydrogen atom from hydrogen, methane, and ethane by the cyanoethynyl radical (k(H2):k(CH4):k(C2H6) = 1:9.3:63). Implications of these results for the proposal that hydrogen abstraction plays an important role in the conversion of methane to ethane and in the protection of unsaturated compounds from photoconsumption in the atmosphere of Titan are discussed.

Clarke, David W.↗

Investigation of Infra-red and Nonequilibrium Air Radiation

This report summarizes the results obtained during a research program on the infrared radiation of air plasmas conducted in the High Temperature Gasdynamics Laboratory at Stanford University. This program was intended to investigate the masking of infrared signatures by the air plasma formed behind the bow shock of high velocity missiles. Prior to this work, the radiative emission of air plasmas in the infrared had been the object of few experimental investigations, and although several infrared systems were already modeled in radiation codes such as NEQAIR, measurements were required to validate numerical predictions and indicate whether all transitions of importance were accounted for in the model. The program was further motivated by the fact that 9 excited states (A, B, C, D, B', F, H, and H') of NO radiate in the infrared, especially between 1 and 1.5 microns where at least 9 transitions involving can be observed. Because these IR transitions are relatively well separated from each other, excited NO states concentrations can be easily measured, thus providing essential information on excited-state chemistry for use in optical diagnostics or in electronic excitation model validation. Detailed comparisons between measured and simulated spectra are presented.

Kruger, Charles H.↗

High-Velocity Absorption Features in FUSE Spectra of Eta Carinae

Numerous broad (200 to 1000 km/sec) features in the FUSE spectrum (905-1187 A) of eta Carinae are identified as absorption by a forest of high-velocity narrow lines formed in the expanding circumstellar envelope. These features were previously thought to be P-Cygni lines arising in the wind of the central star. The features span a heliocentric velocity range of -140 to -580 km/sec and are seen prominently in low-ionization ground-state transitions (e.g. N I 1134-35, Fe II 1145-42, 1133, 1127- 22, P II 1153, C I 1158) in addition to C III] 1176 A. The high-velocity components of the FUSE transitions have depths about 50% below the continuum. The identifications are consistent with the complex velocity structures seen in ground- and excited-state transitions of Mg I, Mg 11, Fe II, V II, etc observed in STIS/E230H spectra. The origin of other broad features of similar width and depth in the FUSE spectrum, but without low-velocity ISM absorption, are unidentified. However, they are suspected of being absorption of singly-ionized iron-peak elements (e.g. Fe II, V II, Cr II) out of excited levels 1,000 to 20,000 cmE-l above the ground state. The high-velocity features seen in Fe II 1145 are also present in Fe II 1608 (STIS/E140M), but are highly saturated in the latter. Since these transitions have nearly identical log (flambda) (1.998 vs. 2.080), the differences in the profiles are attributable to the different aperture sizes used (30 x 30 arcsec for FUSE, 0.2 x 0.2 arcsec for STIS/E140M). The high-velocity gas appears to be very patchy or has a small covering factor near the central star. Eta Carinae has been observed several times by FUSE over the past three years. The FUSE flux levels and spectral features in eta Car are essentially unchanged over the 2000 March to June 2002 period, establishing a baseline far-UV spectrum in advance of the predicted spectroscopic minimum in 2003.

Sonneborn, G.↗

Correlations in alpha-alpha scattering and semi-classical optical models

We show the equivalence of semi-classical solutions to optical model coupled-channel equations derived from Watson's form of the nucleus-nucleus multiple-scattering series to the Glauber multiple-scattering series. A second-order solution to the semi-classical coupled-channel elastic amplitude is shown to be nearly equivalent to a second-order optical-phase-shift approximation to the Glauber amplitude if the densities of all nuclear excited states are approximated by the ground-state density. Using the Jastrow method to model the two-body density we find an average excited-state density to be of negligible importance in the double-scattering region of alpha-alpha scattering.

NASA Discipline Number 04-10↗

A semiempirical study for the ground and excited states of free-base and zinc porphyrin-fullerene dyads

The ground and excited states of a covalently linked porphyrin-fullerene dyad in both its free-base and zinc forms (D. Kuciauskas et al., J. Phys. Chem. 100 (1996) 15926) have been investigated by semiempirical methods. The excited-state properties are discussed by investigation of the character of the molecular orbitals. All frontier MOs are mainly localized on either the donor or the acceptor subunit. Thus, the absorption spectra of both systems are best described as the sum of the spectra of the single components. The experimentally observed spectra are well reproduced by the theoretical computations. Both molecules undergo efficient electron transfer in polar but not in apolar solvents. This experimental finding is explained theoretically by explicitly considering solvent effects. The tenth excited state in the gas phase is of charge-separated character where an electron is transferred from the porphyrin donor to the fullerene acceptor subunit. This state is stabilized in energy in polar solvents due to its large formal dipole moment. The stabilization energy for an apolar environment such as benzene is not sufficient to lower this state to become the first excited singlet state. Thus, no electron transfer is observed, in agreement with experiment. In a polar environment such as acetonitrile, the charge-separated state becomes the S, state and electron transfer takes place, as observed experimentally. The flexible single bond connecting both the donor and acceptor subunits allows free rotation by ca. +/- 30 degrees about the optimized ground-state conformation. For the charge-separated state this optimized geometry has a maximum dipole moment. The geometry of the charge-separated state thus does not change relatively to the ground-state conformation. The electron-donating properties of porphyrin are enhanced in the zinc derivative due to a reduced porphyrin HOMO-LUMO energy gap. This yields a lower energy for the charge-separated state compared to the free-base dyad.

Bridged Compounds/chemistry↗

Enhanced Reverse Saturable Absorption and Optical Limiting in Heavy-Atom Substituted Phthalocyanines

The reverse saturable absorption and optical limiting response of metal phthalocyaninies can be enhanced by using the heavy-atom effect. Phthalocyanines containing heavy metal atoms, such as In, Sn, and Pb show nearly a factor of two enhancement in the ratio of effective excited-state to ground-state absorption cross sections compared to those containing lighter atoms, such as Al and Si. In an f/8 optical geometry, homogeneous solutions of heavy metal phthalocyanines, at 30% linear transmission, limit 8-ns, 532-nm laser pulses to less than or equal to 3 (micro)J (the energy for 50% probability of eye damage) for incident pulses up to 800 (micro)J.

metal phthalocyanines↗

Energy Levels of C IV: The Polarization Method

In a previous publication [Can. J. Phys. 75, 11 (1997)] we calculated the generalized polarizabilities up to multipole order 3 as well as certain higher-order hyperpolarizabilities for two-electron atoms and ions of Z=2-6 and 10. In this paper we apply some of these results to calculate excited-state energies in three times ionized (lithium-like) carbon. For states with angular momentum L greater than or equal to 3 accurate results are obtained using an asymptotic polarizability expansion that includes nonadiabatic effects. Comparison is made with recent optical measurements, and a critical discussion of the correct form of the expansion is given. In addition, the possibility of very accurate measurements of the fine-structure splitting encourages us to present a table of such splittings to very high accuracy. An appendix contains similar results for lithium-like oxygen and neon ions.

Bhatia, A. K.↗

Simultaneous 100-kHz Acetone Planar Laser-Induced Fluorescence and OH* Chemiluminescence in a Linear Non-Premixed Detonation Channel

Reactant mixing and combustion are investigated in an optically accessible, self-excited linear detonation combustor. The mixing field is captured using 100 kHz planar laser-induced fluorescence (PLIF) imaging of acetone as a tracer in the fuel supply, while 100 kHz chemiluminescence imaging of excited-state hydroxyl (OH*) radicals simultaneously resolves the evolution of the detonation wave. Time sequences are acquired over multiple detonation cycles in each test, with acetone-PLIF images collected along multiple orthogonal planes to reveal the complex three-dimensional topography of the fuel distribution. The instantaneous and phase averaged acetone-PLIF images enable measurement of key fuel injection characteristics, such as the injector recovery time, fuel jet velocity, and refill height for a range of operating conditions. Instantaneous and phase-averaged measurements of acetone-PLIF with the time-coincident OH* chemiluminescence images also reveal a number key features, such as fuel stratification and weak detonation in the injector near field, incomplete combustion and deflagration behind the detonation wave, vitiation and deflagration of reactants ahead of the detonation wave, and fuel and oxidizer recovery time mismatch leading to combustion inefficiency. These measurements significantly enhance the ability to obtain detailed information on the intracycle and intercycle spatiotemporal evolution of the reactant refill process and its coupled effects on the detonation wave structure and propagation.

Propulsion↗

Exclusive η Electro-Production Beam Spin Asymmetry Measurements using CLAS12 at Jefferson Lab

The exploration of nucleon structure and electromagnetic transitions from ground-state to excited-state is a cornerstone of nuclear physics research. Meson electro-production experiments have opened new avenues for investigating these phenomena, particularly in the 12 GeV era at Jefferson Lab with the CLAS12 spectrometer. The ?N final states, accessible only through isospin resonances I = 1/2, provide a unique tool for studying nucleon excitations. By simplifying the analysis and enabling a cleaner extraction of resonance properties compared to the extensively studied ?N final states, ? electroproduction offers a complementary approach to unraveling the structure of excited nucleons. This work presents the first-ever measurement of the beam spin asymmetry (BSA) in exclusive ? electroproduction, covering a previously unexplored kinematic region with 1.6 ? W ? 2.2 GeV. The BSA is extracted from the CLAS12 data using a comprehensive analysis framework that carefully considers the statistical limitations of the data set. The results are compared to predictions from theoretical models, such as the Jülich-Bonn-Washington (JBW) and MAID, as well as compared to previously published cross-section and spin observable results from CLAS and SLAC. Notably, the extracted BSA exhibits discrepancies with the model predictions, highlighting the potential for refining theoretical descriptions of nucleon resonances and their electromagnetic couplings through the incorporation of these new data. The high precision data obtained in this previously unmeasured kinematic region now serve as valuable input for theorists to refine their models.

Illari, Isabella↗

Exploring the Photophysics of N-Type Polymer N2200

The polymer interphase is a complex environment comprised of polymer chains, solvent molecules, and electrolyte ions. However, the microenvironments that these ingredients produce is both poorly-understood and difficult to investigate given the system's inherent structural heterogeneity. Nonetheless, a fundamental understanding of the structure, electrochemical behavior, and excited-state dynamics is a key prerequisite to optimizing devices based on such a system - for instance, photoelectrochemical cells for the direct, light-driven production of solar hydrogen, which may minimize efficiency losses compared to sequential light harvesting and electrochemical hydrogen production in separate but linked devices. This work combines transient absorption (TA) spectroscopy, which is a powerful tool for the observation of a variety of excited states on a femto- to microsecond timescale, with time-resolved microwave conductivity (TRMC) spectroscopy, which selectively probes the dynamics of free charge carriers (FC), of a blend of a donor polymer (PTB7-Th) and acceptor polymer (N2200) in a bulk heterojunction. Initial results indicate an extension of FC lifetime and homogenization of the microenvironment on a whole-film level, not just at the surface of the polymer; however, many questions are still under active investigation, including the changes in energy of the involved polaron states, effective conjugation length, FC mobility and migration distance, etc. Additional experiments regarding the photoinitiated behavior of the blend in different environments and on different timescales are ongoing.

charge recombination↗

Dissipation Enables Strongly Detuning-Dependent Interference in Pulsed Dynamical Decoupling

One of the defining features of pulsed dynamical decoupling is its suppression of a driven qubit's sensitivity to static detuning errors between the drive field and qubit resonance. In this paper, we show that dissipation, in the form of excited-state decay, can change this behavior entirely, producing an interference signal with a strong detuning dependence. This signal arises from decay during driven evolution and relies on coherence retained by the qubit after such a decay event. We develop analytical and numerical models that capture the underlying mechanism and observe this same dissipation-induced detuning dependence experimentally in both a free-space strontium atom interferometer and a superconducting transmon qubit system. We also use this dissipation-induced detuning dependence as the basis for a new spectroscopic technique called Dissipative Carr-Purcell Spectroscopy (DCPS) and compare it with a traditional Ramsey sequence. Our results establish a regime of pulsed dynamical decoupling in which dissipation reshapes, rather than merely degrades, coherent control, and we expect these dynamics to be relevant to a wide range of quantum systems.

DeRose, Kenneth [Northwestern U.; Fermilab] (ORCID↗

Zinc(II) Monomeric, Dimeric, and Trimeric Photosensitizers with Microsecond‐Lived Intra‐ligand Charge Transfer Excited States Investigated through Time‐Resolved Optical and X‐Ray Spectroscopy

Zn II photosensitizers relative to Cu I complexes have received less attention due to their energetically higher metal‐to‐ligand charge transfer states. Three Zn II complexes, namely a Monomer, a bimetallic helicate, and a trimetallic helicate, bearing phenanthroline ligands are hereby studied through time‐resolved X‐ray absorption (tr‐XAS) and femto‐microsecond optical transient absorption spectroscopy (OTA). The formation of intraligand singlet charge transfer ( I ILCT) excited states is achieved within femtoseconds, followed by intersystem crossing (ISC) in nanoseconds to generate microsecond‐lived triplet ( 3 ILCT) states. Femtosecond OTA shows that the 1 ILCT states in the Monomer, Dimer, and Trimer occur within 235 fs, 683 fs, and 730 fs, respectively, while nano‐microsecond OTA and tr‐XAS show their 3 ILCT states to decay within 1.00 µs, 1.48 µs, and 1.51 µs. The ISC from the 1 ILCT to the 3 ILCT state for the Trimer is 42.8 ns compared to the Monomer and Dimer with ISC rates of less than 13 ns. These differences arise due to the stabilization by π‐π and CH‐π noncovalent interactions of the phenanthroline ligands. The dihedral and torsional angles indicate stronger ligand strains in the excited states of the Dimer and Trimer versus the Monomer. DFT calculations for the electrochemical oxidation potentials further highlight their capability in inducing photoredox processes.

earth-abundant Zn-based photosensitizers↗

Nanorod Pair Complexes Manipulated via Magnetic Casimir Forces

Here, we demonstrate a route to modulate Casmir–Lifshitz interactions between anisotropic nanoparticles and magnetic fluids. By semiclassical quantum electrodynamics, we study ground state dispersion forces for cylindrical dielectric nanorods made of polystyrene (PS) and zinc oxide (ZnO) embedded in toluene-based host media with gold-coated magnetite nanoparticles and also predict magnetic contributions to the fully retarded excited state interaction. The variation in magnetic permeability enables tuning between repulsive and attractive interactions, and measurable magnetic Casimir traps are predicted between a pair of ZnO–PS nanoparticles whose equilibrium position can be modulated over an order of magnitude with a small variation in the size of the magnetite nanoparticle. This provides an alternative magnetic Casimir-effect pathway to reversibly tune quantum electromagnetic forces at the nanoscale for the assembly and enhancement of colloidal stability.

Excited-state interaction↗

Modulating Mid-Gap Electronic States Through Site-Selective Modification in B-Pbx/B'-CuyV2O5/CdS Heterostructures for Photocatalytic Hydrogen Evolution

We interfaced ..beta..-Pbx/..beta..'-CuyV2O5 compounds, with varying stoichiometries of precisely positioned Pb-ions (x) and Cu-ions (y) in interstitial sites along a tunnel-structured ?-V2O5 framework, with cysteine-capped CdS (cysCdS) quantum dots (QDs) to yield heterostructured photocatalysts. ..beta..-Pbx/..beta..'-CuyV2O5 compounds exhibit midgap electronic states with orbital contributions from both Cu 3d and stereochemically active Pb 6s states that show distinctive light-initiated reactivity with photoexcited QDs. ..beta..-Pbx/..beta..'-CuyV2O5/CdS heterostructures were prepared by linker-assisted assembly (LAA). Scanning and transmission electron microscopy, energy-dispersive X-ray spectroscopy, and Raman spectroscopy revealed that cysCdS QDs were deposited onto surfaces of ..beta..-Pbx/..beta..'-CuyV2O5 via LAA. HAXPES revealed that the site-selective positioning of Pb-ions and Cu-ions promoted close energetic alignment of the midgap states of ..beta..-Pbx/..beta..'-CuyV2O5 compounds with the valence-band maximum of cysCdS QDs. Transient absorption spectroscopy revealed that photogenerated holes were transferred from CdS QDs to midgap states of ..beta..-Pbx/..beta..'-CuyV2O5 compounds on time scales <50 ps. Finally, photoelectrochemical and photochemical experiments revealed that ..beta..-Pbx/..beta..'-CuyV2O5/CdS heterostructures promoted the photocatalytic reduction of H+ to H2. In photoelectrochemical experiments, under oxidative conditions, for all ..beta..-Pbx/..beta..'-CuyV2O5/CdS heterostructures, H2 was evolved at a Pt counter electrode while a sacrificial donor was oxidized at the heterostructure-functionalized working electrode. In contrast, under reductive conditions, for ..beta..-Pb0.152V2O5/CdS and ..beta..-Pbx/..beta..'-CuyV2O5/CdS heterostructures, H2 was evolved at the working electrode. In photochemical experiments, dispersed ..beta..-Pbx/..beta..'-CuyV2O5/CdS heterostructures promoted the reduction of H+ to H2 under white-light illumination; ..beta..'-Cu0.55V2O5/CdS and ..beta..-Pbx/..beta..'-CuyV2O5/CdS heterostructures, for which midgap states have Cu 3d orbital character, generated 2-fold more H2 than ..beta..-Pb0.152V2O5/CdS heterostructures. Cu-ion insertion thus appends additional acceptor surface states that improve ligand-mediated hole transfer from photoexcited QDs, but such states are intrinsically limited in mediating hole transport to the substrate as a result of the low mobility of holes in narrow Cu 3d-states. Our results reveal that the density and orbital character of midgap states of ..beta..-Pbx/..beta..'-CuyV2O5 compounds, tunable through recently developed site-selective ion insertion strategies, determine efficiencies of charge-transfer and charge-transport mechanisms that underpin photocatalysis.

36 MATERIALS SCIENCE↗

Amplified Spontaneous Emission from Electron–Hole Quantum Droplets in Colloidal CdSe Nanoplatelets

Two-dimensional cadmium selenide nanoplatelets (NPLs) exhibit large absorption cross sections and homogeneously broadened band-edge transitions that offer utility in wide-ranging optoelectronic applications. Here, we examine the temperature-dependence of amplified spontaneous emission (ASE) in 4- and 5-monolayer thick NPLs and show that the threshold for close-packed (neat) films decreases with decreasing temperature by a factor of 2-10 relative to ambient temperature owing to extrinsic (trapping) and intrinsic (phonon-derived line width) factors. Interestingly, for pump intensities that exceed the ASE threshold, we find development of intense emission to lower energy in particular provided that the film temperature is <= 200 K. For NPLs diluted in an inert polymer, both biexcitonic ASE and low-energy emission are suppressed, suggesting that described neat-film observables rely upon high chromophore density and rapid, collective processes. Transient emission spectra reveal ultrafast red-shifting with the time of the lower energy emission. Taken together, these findings indicate a previously unreported process of amplified stimulated emission from polyexciton states that is consistent with quantum droplets and constitutes a form of exciton condensate. For studied samples, quantum droplets form provided that roughly 17 meV or less of thermal energy is available, which we hypothesize relates to polyexciton binding energy. Polyexciton ASE can produce pump-fluence-tunable red-shifted ASE even 120 meV lower in energy than biexciton ASE. Finally, our findings convey the importance of biexciton and polyexciton populations in nanoplatelets and show that quantum droplets can exhibit light amplification at significantly lower photon energies than biexcitonic ASE.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗