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At least 127 records · Page 7

A Mg2+-Ge4+ substituting strategy for optimizing color rendering index and luminescence of YAG: Ce3+ phosphors for white LEDs

Highlights: • Mg{sup 2+}-Ge{sup 4+} ion pairs can partially substitute the Al{sup 3+} ions of YAG successfully. With the substitution, the garnet crystal structure remains unchanged. • With increasing Mg{sup 2+}-Ge{sup 4+} ions concentrations, the emission spectra show a progressive red-shift, from 528 to 552 nm (about 24 nm). • In white LEDs, with increasing Mg{sup 2+}-Ge{sup 4+} ions concentrations, the CCT decreased gradually from 6798 to 3261 K and the CRI increased from 76.5 to 89.3. - Abstract: Mg{sup 2+}-Ge{sup 4+} ions substituted YAG: Ce{sup 3+} phosphors (Y{sub 3}Al{sub 5-2x}Mg{sub x}Ge{sub x}O{sub 12}: Ce{sup 3+}) were prepared by high temperature solid state reaction method. X-ray diffraction (XRD), Scanning election microscope (SEM), Photoluminescence (PL) spectra and so on were used to characterize the samples. The effects of Mg{sup 2+}-Ge{sup 4+} concentrations on the morphology, structure, luminescence properties, fluorescence lifetime and white LED performance of YAG: Ce{sup 3+} phosphors were studied in detail. The results indicate that Mg{sup 2+}-Ge{sup 4+} ion pairs can partially substitute the Al{sup 3+} ions of YAG successfully. With the substitution, the garnet crystal structure remains unchanged. However the emission spectra show a progressive red-shift, from 528 to 552 nm (about 24 nm). The lifetime decreased rapidly from 84 to 26 ns. In particular, the correlated color temperature (CCT) decreases gradually from 6798 to 3261 K and the color rendering index (CRI) increases from 76.5 to 89.3 with the increasing of the incorporation content of Mg{sup 2+}-Ge{sup 4+} ion pairs.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Communication: Broad manifold of excitonic states in light-harvesting complex 1 promotes efficient unidirectional energy transfer in vivo

In photosynthetic organisms, the pigment-protein complexes that comprise the light-harvesting antenna exhibit complex electronic structures and ultrafast dynamics due to the coupling among the chromophores. In this work, we present absorptive two-dimensional (2D) electronic spectra from living cultures of the purple bacterium, Rhodobacter sphaeroides , acquired using gradient assisted photon echo spectroscopy. Diagonal slices through the 2D lineshape of the LH1 stimulated emission/ground state bleach feature reveal a resolvable higher energy population within the B875 manifold. The waiting time evolution of diagonal, horizontal, and vertical slices through the 2D lineshape shows a sub-100 fs intra-complex relaxation as this higher energy population red shifts. The absorption (855 nm) of this higher lying sub-population of B875 before it has red shifted optimizes spectral overlap between the LH1 B875 band and the B850 band of LH2. Access to an energetically broad distribution of excitonic states within B875 offers a mechanism for efficient energy transfer from LH2 to LH1 during photosynthesis while limiting back transfer. Two-dimensional lineshapes reveal a rapid decay in the ground-state bleach/stimulated emission of B875. This signal, identified as a decrease in the dipole strength of a strong transition in LH1 on the red side of the B875 band, is assigned to the rapid localization of an initially delocalized exciton state, a dephasing process that frustrates back transfer from LH1 to LH2.

14 SOLAR ENERGY↗

High-Performance Blue-Excitable Yellow Phosphor Obtained from an Activated Solvochromic Bismuth-Fluorophore Metal–Organic Framework

Here, we report the synthesis, structure, and photoluminescence properties of a new bismuth based luminescent metal-organic framework (LMOF). The framework is comprised of a 9-coordinated Bi 3+ building unit and 4', 4''', 4''''', 4'''''''-(ethene-1,1,2,2-tetrayl)tetrakis([1,1'-biphenyl]-4-carboxylic acid) (H 4 tcbpe) organic linker, which has strong yellow aggregation induced emission (AIE). The structure can be viewed as two interpenetrated 4,4-anionic nets that are stabilized by K + ions forming one-dimensional helical inorganic chains by connecting bismuth nodes through shared oxygen bonds. The as-made LMOF has a bluish emission centered at 459 nm with an internal quantum yield of 57% when excited at 360 nm. The emission properties of the LMOF were found to be highly solvochromic with respect to DMF. Upon partial solvent removal, the framework undergoes significant red-shifting to a greenish emission centered at 500 nm. Complete removal of DMF results in additional red-shifting fluorescence coupled with structural changes. The resulting material has strong blue-excitable (455 nm) yellow emission centered at 553 nm, with a quantum yield of 74%, which is maintained after heating in air for 5 days at 90°C. This is the second highest quantum yield value for blue-excited yellow emission among all reported LMOFs.

36 MATERIALS SCIENCE↗

A search for N-type galaxies

A large number of distant clusters of galaxies was examined for the presence of a bright compact galaxy or blue stellar object. Nearly 600 square degrees of sky were searched using glass copies of the National Geographic Society-Palomar Observatory Sky Survey plates, and over 20 fields were selected for observation. The objects were examined for infrared and ultraviolet excesses, using wideband filter photography and spectroscopy. Initial findings include a faint, distant cluster of galaxies near the quasi-stellar radio source 4C 37.43 with a red shift of 0.370. One of these galaxies has an emission line at 6895 A, indicating a possible red shift of 0.377 of the 5007 A line of (0 III).

Jefferies, J. T.↗

X-ray absorption and high redshift quasars

The low energy cut-offs toward radio-loud quasars with z greater than 2, red quasars, and broad absorption line quasars are discussed. The X-ray absorption seems to be common among different types of red shift quasar. The Rosat position sensitive proportional counter (PSPC) spectra of z = 3 quasars and of a red quasar are presented. Broad absorption lines show outflow velocities of up to 0.1 c to 0.2 c. The advantages and the disadvantages of high red shift observations are underlined.

Elvis, Martin↗

High resolution spectroscopy of jet cooled phenyl radical: The ν{sub 1} and ν{sub 2} a{sub 1} symmetry C–H stretching modes

A series of CH stretch modes in phenyl radical (C{sub 6}H{sub 5}) has been investigated via high resolution infrared spectroscopy at sub-Doppler resolution (∼60 MHz) in a supersonic discharge slit jet expansion. Two fundamental vibrations of a{sub 1} symmetry, ν{sub 1} and ν{sub 2}, are observed and rotationally analyzed for the first time, corresponding to in-phase and out-of-phase symmetric CH stretch excitation at the ortho/meta/para and ortho/para C atoms with respect to the radical center. The ν{sub 1} and ν{sub 2} band origins are determined to be 3073.968 50(8) cm{sup −1} and 3062.264 80(7) cm{sup −1}, respectively, which both agree within 5 cm{sup −1} with theoretical anharmonic scaling predictions based on density functional B3LYP/6-311g++(3df,3dp) calculations. Integrated band strengths for each of the CH stretch bands are analyzed, with the relative intensities agreeing remarkably well with theoretical predictions. Frequency comparison with previous low resolution Ar-matrix spectroscopy [A. V. Friderichsen et al., J. Am. Chem. Soc. 123, 1977 (2001)] reveals a nearly uniform Δν ≈ + 10-12 cm{sup −1} blue shift between gas phase and Ar matrix values for ν{sub 1} and ν{sub 2}. This differs substantially from the much smaller red shift (Δν ≈ − 1 cm{sup −1}) reported for the ν{sub 19} mode, and suggests a simple physical model in terms of vibrational mode symmetry and crowding due to the matrix environment. Finally, the infrared phenyl spectra are well described by a simple asymmetric rigid rotor Hamiltonian and show no evidence for spectral congestion due to intramolecular vibrational coupling, which bodes well for high resolution studies of other ring radicals and polycyclic aromatic hydrocarbons. In summary, the combination of slit jet discharge methods with high resolution infrared lasers enables spectroscopic investigation of even highly reactive combustion and interstellar radical intermediates under gas phase, jet-cooled (T{sub rot} ≈ 11 K) conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Excited States of Light-Harvesting Systems Based on Fullerene/Graphene Oxide and Porphyrin/Smaragdyrin

In this work, we present a theoretical study at the density functional theory (DFT) level and time-dependent DFT of the ground and singlet excited states of electron donor–acceptor complexes formed by porphyrin (TPP)/smaragdyrin (TPOS) (expanded porphyrin), as light-harvesting systems, and fullerene (C 60 )/graphene oxide (GO), as acceptor nanocarbon structure. We investigate the effect of the nanocarbon on UV–vis electronic absorption of porphyrin/smaragdyrin, using the functionals B3LYP, PBE, M06, and wB97XD. The results showed the lowest deviation of the Q-band for the functional M06 (0.01–0.02 eV). Electronic absorption spectra calculated for the complexes with M06 predict that (a) graphene oxide increases the intensity of the Soret band, (b) fullerene produces a red-shift of the Q bands (4 nm) with respect to graphene oxide, and (c) smaragdyrin causes a red-shift of Q (27–48 nm) and Soret (37 nm) absorption bands as compared to porphyrin. We also investigate the effect of the nanocarbon structure on the charge-transfer (CT) excited states. Using the perturbative delta-SCF method with the PBE functional, we found that the charge-transfer excitation energy increases as TPOS-C 60 (2.53 eV) < TPP-GO (2.89 eV) < TPP-C 60 (3.01 eV) < TPOS-GO (3.28 eV). The presence of a nanocarbon structure affects more strongly smaragdyrin (~0.8 eV) than porphyrin (~0.1 eV). We show that the binding between smaragdyrin and fullerene C 60 favors the charge separation states with a lower energy cost, which means that these systems present an advantage for its application in photovoltaic cells.

36 MATERIALS SCIENCE↗

The non-uniform early structural response of globular proteins to cold denaturing conditions: A case study with Yfh1

The mechanism of cold denaturation in proteins is often incompletely understood due to limitations in accessing the denatured states at extremely low temperatures. Using atomistic molecular dynamics simulations, we have compared early (nanosecond timescale) structural and solvation properties of yeast frataxin (Yfh1) at its temperature of maximum stability, 292 K (T{sub s}), and the experimentally observed temperature of complete unfolding, 268 K (T{sub c}). Within the simulated timescales, discernible “global” level structural loss at T{sub c} is correlated with a distinct increase in surface hydration. However, the hydration and the unfolding events do not occur uniformly over the entire protein surface, but are sensitive to local structural propensity and hydrophobicity. Calculated infrared absorption spectra in the amide-I region of the whole protein show a distinct red shift at T{sub c} in comparison to T{sub s}. Domain specific calculations of IR spectra indicate that the red shift primarily arises from the beta strands. This is commensurate with a marked increase in solvent accessible surface area per residue for the beta-sheets at T{sub c}. Detailed analyses of structure and dynamics of hydration water around the hydrophobic residues of the beta-sheets show a more bulk water like behavior at T{sub c} due to preferential disruption of the hydrophobic effects around these domains. Our results indicate that in this protein, the surface exposed beta-sheet domains are more susceptible to cold denaturing conditions, in qualitative agreement with solution NMR experimental results.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Shift and width measurements of the Stark-broadened ionized helium line at 1215 A

Time-resolved photoelectric measurements were made of the shifts of helium plasma lines at 1640 A and 1215 A and of the Stark profile of the 1215 A line, using an electromagnetic shock tube as a light source. These red shifts are consistent with a plasma polarization shift, where the interaction energy between the radiating ion and the perturbing plasma electrons corresponds to the Coulomb interaction near the excited state Bohr radius. No significant shifts were observed for the 1640 A line, while the 1215 A line underwent a red shift of about 0.5 A. The measured Stark width of the 1215 A line was 10-45% greater than the calculated width based on the measured width of the 4686 A line.

Van Zandt, J. R.↗

A Vibrational Probe of Electrical Doping in N2200 and Fermi-Level Alignment at Polymer Cathode/Metal Cocatalyst/Electrolyte Junctions

Hybrid (photo)­cathodes consisting of conjugated polymer and hydrogen evolution reaction (HER) cocatalysts are an emerging platform for low-cost solar fuel generation. Poly­{[N,N′-bis­(2-octyldodecyl)-naphthalene-1,4,5,8-bis­(dicarboximide)-2,6-diyl]-alt-5,5′-(2,2′-bithiophene)}, known as P­(NDI2OD-T2) or N2200, is a promising electron accepting material for bulk heterojunction photocathodes. Unlike inorganic (photo)­electrodes, much less is known about the energetic alignment of conjugated polymer electrode/metal/electrolyte junctions. Here, in this work, we investigate the electrical doping behavior in an N2200 cathode and its Fermi-level alignment with gold nanoparticles, which is used here as a model for the hydrogen evolution metal cocatalyst. Through UV/visible, Raman, and attenuated total-reflectance infrared spectroelectrochemistry, we observe the impact of electrical doping on the vibrational frequencies of neutral, anion, and dianion species in N2200, which suggests that electron density changes within the corresponding naphthalene-diimide (NDI) units. Upon one-electron reduction, the $C=O$ stretching frequency of the NDI anion unit (polaron) shows a red shift by ∼ 68 cm –1 . Additionally, the $C=O$ stretching frequency of neutral units in the doped N2200 shows a minor red shift of ∼ 5 cm –1 , suggesting charge transfer from neighboring polaron units. Surface-enhanced Raman spectroscopy measurements of a gold nanoparticle-functionalized N2200 electrode revealed that the Au Fermi level only shifts with that of N2200 upon polaron formation; thus, the formal potential of polymer polaron formation determines the behavior of the catalyst Fermi level, which we posit will modulate reaction capability. This mechanistic study provides a new approach for understanding the nanometer-scale energetics at the conjugated polymer/cocatalyst junction and provides critical insights for the future design of HER (photo)­cathodes.

charge transfer↗

Synthesis, characterization and optical properties of hybrid PVA–ZnO nanocomposite: A composition dependent study

Graphical abstract: - Highlights: • ZnO nanoparticles were prepared by solution combustion method. • PVA–ZnO nanocomposites were synthesized by solution casting method. • Doped and undoped films were characterized using different techniques. • Red shift in optical band gap was observed in Nanocomposite films with respect to nano ZnO. • Photoluminescence intensity was found to be optimum for PVA–10 mol% ZnO nanocomposite film. - Abstract: Nanocomposites of poly vinyl alcohol (PVA) and ZnO have been synthesized using the solution casting technique for different concentrations of nano ZnO powder prepared by low temperature solution combustion method. The formation of polymer nanocomposite and changes in the structural and micro structural properties of the materials were investigated by X-ray diffraction, Energy dispersive X ray spectroscopy and optical microscopy techniques (FTIR and UV–Visible). The surface morphology of PVA–ZnO nanocomposite films were elucidated using Scanning Electron Microscopy. The optical absorption spectrum of nano ZnO shows blue shift in the optical band gap energy with respect to characteristic bulk ZnO at room temperature, whereas PVA–ZnO hybrid films show red shift with respect to nano ZnO. The photoluminescence studies show that the intensity of the blue emission (470 nm) varies with change in concentration of ZnO with an optimum intensity observed at 10 mol% of ZnO.

36 MATERIALS SCIENCE↗

Trace Key Mechanistic Features of the Arsenite Sequestration Reaction with Nanoscale Zerovalent Iron

Nanoscale zerovalent iron (nZVI) is considered as a highly efficient material for sequestrating arsenite, but the origin of its high efficacy as well as the chemical transformations of arsenite during reaction is not well understood. Here, in this study, we report an in situ X-ray absorption spectroscopy (XAS) study to investigate the complex mechanism of nZVI reaction with arsenite under anaerobic conditions at the time scale from seconds to days. The time-resolved XAS analysis revealed a gradual oxidation of As III to As V in the course of minutes to hours in both the solid and liquid phase for the high (above 0.5 g/L) nZVI dose system. When the reaction time increased up to 60 days, As V became the dominant species. The quick-scanning extended X-ray absorption fine structure (QEAXFS) was introduced to discover the transient intermediate at the highly reactive stage, and a small red-shift in As K-edge absorption edge was observed. The QEAXFS combined with density functional theory (DFT) calculation suggested that the red-shift is likely due to the electron donation in a Fe-O-As complex and possible active sites of As sequestrations include Fe(OH) 4 and 4-Fe cluster. This is the first time that the transient reaction intermediate was identified in the As-nZVI sequestration system at the fast-reacting early stage. This study also demonstrated usefulness of in situ monitoring techniques in environmental water research.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Gamma ray bursts: A review of recent high-precision measurements

Recent measurements and discoveries in gamma ray bursts and transients are reviewed including observations of the red shifted annihilation line in two kinds of slow transients (in 'classical' gamma ray bursts and in the unique 1979 March 5th event); of red shifted nuclear lines in a slow transient and in one gamma ray burst; and of the positions of precise source locations of gamma ray bursts and of the March 5th event, within the supernova remnant N49 in the Large Magellanic Cloud.

Cline, T. L.↗

Time-Dependent Complete Active Space Embedded in Polarizable Force Field

Electron correlation and environmental effects play important roles in electron dynamics and spectroscopic observables of chemical systems in condensed phase. In this paper, we present a time-dependent complete active space configuration interaction (TD-CASCI) approach embedded in a polaraizable force filed, MMPol. The present implementation of TD-CASCI/MMPol utilizes a direct matrix-vector contraction, allowing studies of large systems. This scheme is used to study the solvatochromic shift of coumarin 153 in methanol. The TD-CASCI/MMPol approach captures the double excitation character in the excited state wave function and accurately predicts the solvatochromic red-shift of coumarin 153 dye within the experimental range, outperforming linear response time-dependent density functional theory. The effect of using different reference orbitals for the TD-CASCI/MMPol simulation is also investigated, highlighting the need for an unbiased treatment of all electronic states in the energy range of interest.

Liu, Hongbin↗

Geometrical parameters effects on local electric field enhancement of silver-dielectric-silver multilayer nanoshell

The local electric field enhancement at different points of silver-dielectric-silver nanoshell is investigated using quasi-static theory. Because of the symmetric and anti-symmetric coupling between surface plasmon of inner silver core and outer silver shell, the local electric field spectrum of silver-dielectric-silver has two distinct peaks at resonance wavelengths. The silver core size and middle dielectric thickness affect the local electric field enhancement at different points of silver-dielectric-silver nanoshell. Increasing the silver core radius always leads to blue shift of shorter resonance wavelength and red shift of longer resonance wavelength. We observed two distinct local electric field peaks, which are corresponded to the symmetric and anti-symmetric coupling between inner and outer surface plasmons. In a system with thick silver shell, local electric field enhancement is greater than a system with thin silver shell. However, the local electric field variations as a function of silver core radius in both systems are different at different points of nanoshell. The effects of the dielectric thickness variations on local electric field are different from those from silver core size variations. As the dielectric thickness is about 3 nm, the highest local electric field enhancement occurs at the surface of the inner silver core, where the symmetric and anti-symmetric modes are mixed together.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Non-radiative relaxation and rectification behavior of metal/semiconductor tetrapod heterostructures

The metal-semiconductor hetero-structures have recently emerged as functional materials for their potential applications in the areas of photonic, optoelectronic, and other fields. Here, we discuss the structural characterization of Au/CdSe tetrapod hetero-structures by using high-resolution transmission electron microscope, high angle annular dark field-scanning transmission electron microscopic, and X-ray diffraction. The blue shifting of the plasmonic band and red shifting of the excitonic band suggest a strong surface plasmon-exciton interaction between Au and CdSe in Au/CdSe tetrapod heterostructure. A significant photoluminescence quenching (83.4%) of CdSe nanorod (NR) is observed in the presence of Au nanoparticle in Au/CdSe tetrapod heterostructure. The radiative and nonradiative decay rates of CdSe nanorods are found to be modified in Au/CdSe tetrapod structures and the nonradiative rate changes from 1.91 × 10{sup 7} s{sup −1} to 9.33 × 10{sup 9} s{sup −1} for CdSe NR to Au/CdSe tetrapod structure, respectively. Current-voltage characteristics of Au/CdSe heterostructure exhibit the rectification property with a threshold voltage of about 0.85 V and the rectifying ratio is 140 which can open up avenues for developing challenging devices.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Structural comparison of allophycocyanin variants reveals the molecular basis for their spectral differences

Abstract Allophycocyanins are phycobiliproteins that absorb red light and transfer the energy to the reaction centers of oxygenic photosynthesis in cyanobacteria and red algae. Recently, it was shown that some allophycocyanins absorb far-red light and that one subset of these allophycocyanins, comprising subunits from the ApcD4 and ApcB3 subfamilies (FRL-AP), form helical nanotubes. The lowest energy absorbance maximum of the oligomeric ApcD4-ApcB3 complexes occurs at 709 nm, which is unlike allophycocyanin (AP; ApcA-ApcB) and allophycocyanin B (AP-B; ApcD-ApcB) trimers that absorb maximally at ~ 650 nm and ~ 670 nm, respectively. The molecular bases of the different spectra of AP variants are presently unclear. To address this, we structurally compared FRL-AP with AP and AP-B, performed spectroscopic analyses on FRL-AP, and leveraged computational approaches. We show that among AP variants, the α-subunit constrains pyrrole ring A of its phycocyanobilin chromophore to different extents, and the coplanarity of ring A with rings B and C sets a baseline for the absorbance maximum of the chromophore. Upon oligomerization, the α-chromophores of all AP variants exhibit a red shift of the absorbance maximum of ~ 25 to 30 nm and band narrowing. We exclude excitonic coupling in FRL-AP as the basis for this red shift and extend the results to discuss AP and AP-B. Instead, we attribute these spectral changes to a conformational alteration of pyrrole ring D, which becomes more coplanar with rings B and C upon oligomerization. This study expands the molecular understanding of light-harvesting attributes of phycobiliproteins and will aid in designing phycobiliproteins for biotechnological applications.

Gisriel, Christopher J.↗

Photoluminescence Dynamics Defined by Exciton Trapping Potential of Coupled Defect States in DNA-Functionalized Carbon Nanotubes

Chemical reactions between semiconducting single-wall carbon nanotubes (SWCNTs) and single-stranded DNA (ssDNA) achieve spatially patterned covalent functionalization sites and create coupled fluorescent quantum defects on the nanotube surface, tailoring SWCNT photophysics for applications such as single-photon emitters in quantum information technologies. The evaluation of relaxation dynamics of photoluminescence (PL) from those coupled quantum defects is essential for understanding the nanotube electronic structure and beneficial to the design of quantum light emitters. Here, we measured the PL decay for ssDNA-functionalized SWCNTs as a function of the guanine content of the ssDNA oligo that dictates the red-shifting of their PL emission peaks relative to the band-edge exciton. We then correlate the observed dependence of PL decay dynamics on energy red-shifts to the exciton potential energy landscape, which is modeled using first-principles approaches based upon the morphology of ssDNA-altered SWCNTs obtained by atomic force microscopy (AFM) imaging. In this work, our simulations illustrate that the multiple guanine defects introduced within a single ssDNA strand strongly interact to create a deep exciton trapping well, acting as a single hybrid trap. The emission decay from the distinctive trapping potential landscape is found to be biexponential for ssDNA-modified SWCNTs. We attributed the fast time component of the biexponential PL decay to the redistribution of exciton population among the lowest energy bright states and a manifold of dark states emerging from the coupling of multiple guanine defects. The long lifetime component in the biexponential decay, on the other hand, is attributed to the redistribution of exciton population among different exciton trapping sites that arise from the binding of multiple ssDNA strands along the nanotube axis. AFM measurements indicate that those trapping sites are separated on average by ~8 nm along the nanotube axis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗