Engineering of a calcium-ion binding site into the RC-LH1-PufX complex of Rhodobacter sphaeroides to enable ion-dependent spectral red-shifting
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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
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Results for “RED SHIFT”
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Communication: Towards the binding energy and vibrational red shift of the simplest organic hydrogen bond: Harmonic constraints for methanol dimer
The discrepancy between experimental and harmonically predicted shifts of the OH stretching fundamental of methanol upon hydrogen bonding to a second methanol unit is too large to be blamed mostly on diagonal and off-diagonal anharmonicity corrections. It is shown that a decisive contribution comes from post-MP2 electron correlation effects, which appear not to be captured by any of the popular density functionals. We also identify that the major deficiency is in the description of the donor OH bond. Together with estimates for the electronic and harmonically zero-point corrected dimer binding energies, this work provides essential constraints for a quantitative description of this simple hydrogen bond. The spectroscopic dissociation energy is predicted to be larger than 18 kJ/mol and the harmonic OH-stretching fundamental shifts by about −121 cm{sup −1} upon dimerization, somewhat more than in the anharmonic experiment (−111 cm{sup −1})
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Quantitative relationship between clock gravitational 'red-shift' violations and nonuniversality of free-fall rates in nonmetric theories of gravity
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Nordtvedt, K., Jr.↗
Principles of equivalence, Eotvos experiments, and gravitational red-shift experiments - The free fall of electromagnetic systems to post-post-Coulombian order
Free fall in an external static gravitational field of a composite test body consisting of electromagnetically interacting charged particles is analyzed using the TH-epsilon-mu formalism developed by Lightman and Lee (1973). The Lightman and Lee calculation that was carried out to 'post-Coulombian' order is extended to 'post-post-Coulombian' order, and violations of the weak equivalence principle are found which result from the magnetostatic self-energy of the test body. The current generation of Eotvos experiments is shown to test the cited formalism at first order in the external gravitational potential to an accuracy of 4 by 10 to the -10th power for electrostatic energies and 6 by 10 to the -6th power for magnetostatic energies. It is concluded that although the formalism can be tested to an accuracy of 0.04 for electrostatic energies at second order in the gravitational potential, a significant second-order test for magnetostatic energies would require Eotvos experiments accurate to better than one part in 10 to the 15th power.
Haugan, M. P.↗
Gravitational waves and red shifts - A space experiment for testing relativistic gravity using multiple time-correlated radio signals
A two-step satellite mission for improving the accuracy of gravitational wave detection and for observing actual gravity waveforms is proposed. The spacecraft would carry both a highly stable hydrogen maser, which would control a transmitter sending signals to earth, and a Doppler transponder operating in the two-way mode. The use of simultaneous one- and two-way Doppler transmissions offers four time records of frequency pulsations, which can reveal gravitational radiation at 1-10 MHz with an amplitude accuracy of a factor of six. The first mission phase would consist of a Shuttle launch into a highly eccentric orbit to obtain measurements of the gravitational redshift using gravitational potentials of different earth regions to establish that gravity is describable by a metric theory. Then, after a boost into a heliocentric orbit at 6 AU, the earth-satellite system could detect gravitational waves in the solar system, as well as bursts emitted by the collisions of supermassive black holes.
Smarr, L. L.↗
Red-Shifting and Broadening of Quantum Well Infrared Photodetector's Response via Impurity-Free Vacancy Disordering
The partial intermixing of the well and barrier materials offers unique opportunities to shift locally the bandgap of quantum well structures (QW).
carrent characteristics absolute response quantum ↗
Crystal structure, electronic structure, and photoluminescent properties of SrMoO{sub 4}:Tb{sup 3+} phosphors
Highlights: • SrMoO{sub 4}:Tb{sup 3+} phosphor samples were synthesized at different temperatures. • The crystal and electronic structures, and luminescence properties were studied. • The excitation peak shifts to red with increasing the sintering temperature. • The luminescence mechanism of SrMoO{sub 4}:Tb{sup 3+} was suggested. - Abstract: The experimental and theoretical studies of the optical properties of SrMoO{sub 4}:Tb{sup 3+} phosphors were carried out. The structural, optical, and electronical properties of the phosphors were systematically studied. The phosphor samples were crystallized at different temperatures via a sol–gel method. Excitation spectra of SrMoO{sub 4}:Tb{sup 3+} powder samples exhibited gradual red shift and luminescent intensity changed with increasing the sintering temperature. Such spectral changes depend strongly on the crystallographic properties such as lattice parameters and crystallinity. The shift of the excitation spectra is mainly ascribed to the covalent bond interaction between Mo−O bonds. An energy band model was demonstrated to describe the luminescence mechanism in the material.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Understanding and controlling chromaticity shift in LED devices
Chromaticity shift in light-emitting diode (LED) devices arises from multiple mechanisms, and at least five different chromaticity shift modes (CSMs) have been identified to date. This paper focuses on the impacts of irreversible phosphor degradation as a cause of chromaticity shifts in LED devices. The nitride phosphors used to produce warm white LEDs are especially vulnerable to degradation due to thermal and chemical effects such as reactions with oxygen and water. As a result, LED devices utilizing these phosphors were found to undergo either a green shift or, less commonly, a red shift depending on the phosphor mix in the LED devices. These types of chromaticity shifts are classified as CSM-2 (green shift) and CSM-5 (red shift). This paper provides an overview of the kinetic processes responsible for green and red chromaticity shifts along with examples from accelerated stress testing of 6” downlights. Both CSMs appear to proceed through analogous mechanisms that are initiated at the surface of the phosphor. A green shift is produced by the surface oxidation of the nitride phosphor that changes the emission profile to lower wavelengths. As the surface oxidation reaction proceeds, reactant limitations slow the rate and bulk oxidation processes become more prevalent. We found that a red chromaticity shift arises from quenching of the green phosphor, also possibly due to surface reactions of oxygen, which shift the emission chromaticity in the red direction. In conclusion, we discuss the implications of these findings on projecting chromaticity.
Davis, Lynn↗
Equatorial coordination of uranyl: Correlating ligand charge donation with the O yl -U-O yl asymmetric stretch frequency
In uranyl coordination complexes, UO 2 (L) n 2+ , uranium in the formally dipositive [O=U=O] 2+ moiety is coordinated by n neutral organic electron donor ligands, L. The extent of ligand electron donation, which results in partial reduction of uranyl and weakening of the U=O bonds, is revealed by the magnitude of the red-shift of the uranyl asymmetric stretch frequency, ν 3 . This phenomenon appears in gas-phase complexes in which uranyl is coordinated by electron donor ligands: the ν 3 red-shift increases as the number of ligands and their proton affinity (PA) increases. Because PA is a measure of the enthalpy change associated with a proton-ligand interaction, which is much stronger and of a different nature than metal ion-ligand bonding, it is not necessarily expected that ligand PAs should reliably predict uranyl-ligand bonding and the resulting ν 3 red-shift. In this study, ν 3 was measured for uranyl coordinated by ligands with a relatively broad range of PAs, revealing a surprisingly good correlation between PA and ν 3 frequency. From computed ν 3 frequencies for bare UO 2 cations and neutrals, it is inferred that the effective charge of uranyl in UO 2 (L) n 2+ complexes can be reduced to near zero upon ligation by sufficiently strong charge-donor ligands. The basis for the correlation between ν 3 and ligand PAs, as well as limitations and deviations from it, are considered. It is demonstrated that the correlation evidently extends to a ligand that exhibits polydentate metal ion coordination.
Gibson, John K.↗
When the universe expands too fast: relentless dark matter
Here we consider a modification to the standard cosmological history consisting of introducing a new species φ whose energy density red-shifts with the scale factor a like ρ φ ∝ a -(4+n) . For 0n>, such a red-shift is faster than radiation, hence the new species dominates the energy budget of the universe at early times while it is completely negligible at late times. If equality with the radiation energy density is achieved at low enough temperatures, dark matter can be produced as a thermal relic during the new cosmological phase. Dark matter freeze-out then occurs at higher temperatures compared to the standard case, implying that reproducing the observed abundance requires significantly larger annihilation rates. Here, we point out a completely new phenomenon, which we refer to as relentless dark matter: for large enough n, unlike the standard case where annihilation ends shortly after the departure from thermal equilibrium, dark matter particles keep annihilating long after leaving chemical equilibrium, with a significant depletion of the final relic abundance. Relentless annihilation occurs for n ≥ 2 and n ≥ 4 for s-wave and p-wave annihilation, respectively, and it thus occurs in well motivated scenarios such as a quintessence with a kination phase. We discuss a few microscopic realizations for the new cosmological component and highlight the phenomenological consequences of our calculations for dark matter searches.
79 ASTRONOMY AND ASTROPHYSICS↗
Interplay between Electrostatic Properties of Molecular Adducts and Their Positions at Carbon Nanotubes
Formation of the sp 3 -defect due to covalent functionalization of a single-walled carbon nanotube (SWCNT) results in a new red-shifted emissive excitons. Here, using density functional theory, we study the impact of the intrinsic molecular dipole moments and the local charges induced by various molecular adducts on the energy and localization properties of the optically active defect-based exciton in a (10,5) SWCNT. The interplay of two effects plays a role in the localization of the exciton and, therefore, its red shift, but at different scales: The source of the leading order contribution is the defect conformation, resulting in the red shift of the defect-associated exciton with respect to the E 11 band of the pristine SWCNT on the order of ~100 meV, while the individual dipoles and polarization properties of molecular adducts lead to significantly smaller red shifts on the order of ~10 meV. While the species-dependent trends in defect-induced charges do not directly correlate to the exciton red shift, the charge at the sp 3 -defect exhibits a distinct behavior between ortho- and para-defect configurations and is relevant to the chemical reactivity of the defect position depending on the adduct type. Overall, our computational results may be helpful for diverse synthetic strategies to fine-tune emission of SWCNTs toward desired applications.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
The Second Swift BAT Gamma-Ray Burst Catalog
We present the second Swift Burst Alert Telescope (BAT) catalog of gamma-ray bursts (GRBs), which contains 476 bursts detected by the BAT between 2004 December 19 and 2009 December 21. This catalog (hereafter the BAT2 catalog) presents burst trigger time, location, 90% error radius, duration, fluence, peak flux, time-averaged spectral parameters and time-resolved spectral parametert:; measured by the BAT. In the correlation study of various observed parameters extracted from the BAT prompt emission data, we distinguish among long-duration GRBs (L-GRBs), short-duration GRBs (S-GRBs), and short-duration GRBs with extended emission (S-GRBs with E.E.) to investigate differences in the prompt emission properties. The fraction of L-GRBs, S-GRBs and S-GRBs with E.E. in the catalog are 89%, 8% and 2% respectively. We compare the BAT prompt emission properties with the BATSE, BeppoSAX and HETE-2 GRB samples. We also correlate the observed prompt emission properties with the redshifts for the GRBs with known redshift. The BAT T90 and T50 durations peak at 70 s and 30 s, respectively. We confirm that the spectra of the BAT S-GRBs are generally harder than those of the L-GRBs. The time-averaged spectra of the BAT S GRBs with E.E. are similar to those of the L-GRBs. Whereas, the spectra of the initial short spikes of the S-GRBs with E.E. are similar to those of the S-GRBs. We show that the BAT GRB samples are significantly softer than the BATSE bright GRBs, and that the time-averaged E obs/peak of the BAT GRBs peaks at 80 keV which is significantly lower energy than those of the BATSE sample which peak at 320 keV. The time-averaged spectral properties of the BAT GRB sample are similar to those of the HETE-2 GRB samples. By time-resolved spectral analysis, we find that 10% of the BAT observed photon indices are outside the allowed region of the synchrotron shock model. The observed durations of the BAT high redshift GRBs are not systematically longer than those of the moderate red shift GRBs. Furthermore, the observed spectra of the BAT high red shift GRBs are similar to or harder than the moderate red shift GRBs. The T90 and T50 distributions measured at the 140-220 keY band in the GRB rest frame form the BAT known redshift GRBs peak at 19 sand 8 s, respectively. We also provide an update on the status of the on-orbit BAT calibrations.
Barthelmy, S. D.↗
The luminosity function of quasars and its evolution: A comparison of optically selected quasars and quasars found in radio catalogs
The luminosity function of quasars and its evolution are discussed, based on comparison of available data on optically selected quasars and quasars found in radio catalogs. It is assumed that the red shift of quasars is cosmological and the results are expressed in the framework of the Lambda = 0, Q sub Q = 1 cosmological model. The predictions of various density evolution laws are compared with observations of an optically selected sample of quasars and quasar samples from radio catalogs. The differences between the optical luminosity functions, the red shift distributions and the radio to optical luminosity ratios of optically selected quasars and radio quasars rule out luminosity functions where there is complete absence of correlation between radio and optical luminosities. These differences also imply that Schmidt's (1970) luminosity function, where there exists a statistical correlation between radio and optical luminosities, although may be correct for high red shift objects, disagrees with observation at low red shifts. These differences can be accounted for by postulating existence of two classes (1 and 2) of objects.
Petrosian, V.↗
Widely tunable alloy composition and crystal structure in catalyst-free InGaAs nanowire arrays grown by selective area molecular beam epitaxy
We delineate the optimized growth parameter space for high-uniformity catalyst-free InGaAs nanowire (NW) arrays on Si over nearly the entire alloy compositional range using selective area molecular beam epitaxy. Under the required high group-V fluxes and V/III ratios, the respective growth windows shift to higher growth temperatures as the Ga-content x(Ga) is tuned from In-rich to Ga-rich InGaAs NWs. Using correlated x-ray diffraction, transmission electron microscopy, and micro-photoluminescence spectroscopy, we identify structural defects to govern luminescence linewidths in In-rich (x(Ga) < 0.4) and Ga-rich (x(Ga) > 0.6) NWs, whereas limitations at intermediate Ga-content (0.4 < x(Ga) < 0.6) are mainly due to compositional inhomogeneities. Most remarkably, the catalyst-free InGaAs NWs exhibit a characteristic transition in crystal structure from wurtzite to zincblende (ZB) dominated phase near x(Ga) ∼ 0.4 that is further reflected in a cross-over from blue-shifted to red-shifted photoluminescence emission relative to the band edge emission of the bulk ZB InGaAs phase.
36 MATERIALS SCIENCE↗
Investigating the 3.3 micron infrared fluorescence from naphthalene following ultraviolet excitation
Polycyclic aromatic hydrocarbon (PAH) type molecules are proposed as the carriers of the unidentified infrared (UIR) bands. Detailed studies of the 3.3 micrometer infrared emission features from naphthalene, the simplest PAH, following ultraviolet laser excitation are used in the interpretation of the 3.29 micrometer (3040 cm(sup -1)) UIR band. A time-resolved Fourier transform spectrometer is used to record the infrared emission spectrum of gas-phase naphthalene subsequent to ultraviolet excitation facilitated by an excimer laser operated at either 193 nm or 248 nm. The emission spectra differ significantly from the absorption spectrum in the same spectral region. Following 193 nm excitation the maximum in the emission profile is red-shifted 45 cm(sup -1) relative to the absorption maximum; a 25 cm(sup -1) red-shift is observed after 248 nm excitation. The red-shifting of the emission spectrum is reduced as collisional and radiative relaxation removes energy from the highly vibrationally excited molecules. Coupling between the various vibrational modes is thought to account for the differences between absorption and emission spectra. Strong visible emission is also observed following ultraviolet excitation. Visible emission may play an important role in the rate of radiative relaxation, which according to the interstellar PAH hypothesis occurs only by the slow emission of infrared photons. Studying the visible emission properties of PAH type molecules may be useful in the interpretation of the DIB's observed in absorption.
Williams, Richard M.↗
Further observations of quasi-stellar objects with absorption-line spectra - Ton 1530, PKS 0237-23, and PHL 938.
Quasi-stellar objects with emission line red shifts having multiple absorption line red shifts
Burbidge, E. M.↗
Vertical motions in the quiescent prominences observed in the He I Lambda10830Angstrom line
The observations contain two-dimensional spectral scans of a total of 17 different prominences on the solar disk from the period 3 to 9 May 1981, using the main spectrograph of the solar vacuum telescope at Sacramento Peak. The following conclusions may be drawn from the data: (1) Blue shifts are much more common than red shifts. In many cases more than 90 per cent of the projected prominence area is associated with blue shifts. (2) The darkest prominence regions show the largest blue shift (v less than 3 km s-1). (3) Red shifts are most commonly seen at prominence edges. (4) The general pattern of prominence velocity persists for several hours. On the scale of about 10 arcsec and less, changes are detectable in the course of 2 to 5 minutes. The observed predominance of the blue shifts is largely in agreement with earlier results from H alpha (cf. Martres et al. 1981). It cannot, however, be concluded definitely that the observed shift really represents a net flow of matter. The situation could possibly be analogous to that of the solar transition region where lines such as C IV lambda 1548 angstroms seem to indicate a net inflow, which can hardly be true, at velocities greater than 4 km s(-1) in the quiet Sun (Athay et al. 1983; Gurman and Athay 1983). If the typical structure element of the prominence is sub-resolution, i.e., 2 to 3 arcsec or worse, as in the present case, an apparent net shift could result if the ascending and the decending elements have different temperature and/or pressure. Different lines could then indicate different flow velocities and even opposite directions.
Engvold, Oddbjorn↗
Tunable trimers: Using temperature and pressure to control luminescent emission in gold(I) pyrazolate-based trimers
A systematic investigation into the relationship between the solid-state luminescence and the intermolecular Au∙∙∙Au interactions in a series of pyrazolate-based gold(I) trimers; tris(μ 2 -pyrazolato-N,N')-tri-gold(I) (1), tris(μ 2 -3,4,5-trimethylpyrazolato-N,N')-tri-gold(I) (2), tris(μ 2 -3-methyl-5-phenylpyrazolato-N,N')-tri-gold(I) (3) and tris(μ 2 -3,5-diphenylpyrazolato-N,N')-tri-gold(I) (4) has been carried out using variable temperature and high pressure X-ray crystallography, solid-state emission spectroscopy, Raman spectroscopy and computational techniques. Single-crystal X-ray studies show that there is a significant reduction in the intertrimer Au∙∙∙Au distances both with decreasing temperature and increasing pressure. In the four complexes, the reduction in temperature from 293 to 100 K is accompanied by a reduction in the shortest intermolecular Au∙∙∙Au contacts of between 0.04 and 0.08 Å. The solid-state luminescent emission spectra of 1 and 2 display a red shift with decreasing temperature or increasing pressure. Compound 3 does not emit under ambient conditions but displays increasingly red-shifted luminescence upon cooling or compression. Compound 4 remains emissionless, consistent with the absence of intermolecular Au∙∙∙Au interactions. The largest pressure induced shift in emission is observed in 2 with a red shift of approximately 630 cm -1 per GPa between ambient and 3.80 GPa. The shifts in all the complexes can be correlated with changes in Au∙∙∙Au distance observed by diffraction.
74 ATOMIC AND MOLECULAR PHYSICS↗