Showing papers on "Absorption spectroscopy published in 1997"
TL;DR: The synthesis of epitaxially grown, wurtzite CdSe/CdS core/shell nanocrystals is reported in this paper, where shells of up to three monolayers in thickness were grown on cores ranging in diameter from 23 to 39.
Abstract: The synthesis of epitaxially grown, wurtzite CdSe/CdS core/shell nanocrystals is reported Shells of up to three monolayers in thickness were grown on cores ranging in diameter from 23 to 39 A Shell growth was controllable to within a tenth of a monolayer and was consistently accompanied by a red shift of the absorption spectrum, an increase of the room temperature photoluminescence quantum yield (up to at least 50%), and an increase in the photostability Shell growth was shown to be uniform and epitaxial by the use of X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM), and optical spectroscopy The experimental results indicate that in the excited state the hole is confined to the core and the electron is delocalized throughout the entire structure The photostability can be explained by the confinement of the hole, while the delocalization of the electron results in a degree of electronic accessibility that makes these nanocrystals
2,584 citations
TL;DR: Definitive data on the absorption spectrum of pure water from 380 to 700 nm have been obtained with an integrating cavity technique and several spectroscopic features have been identified in the visible spectrum to the knowledge for the first time.
Abstract: Definitive data on the absorption spectrum of pure water from 380 to 700 nm have been obtained with an integrating cavity technique. The results are in good agreement with those recently obtained by our group with a completely independent photothermal technique. As before, we find that the absorption in the blue is significantly lower than had previously been generally believed and that the absorption minimum is at a significantly shorter wavelength, i.e., 0.0044 ? 0.0006 m(-1) at 418 nm. Several spectroscopic features have been identified in the visible spectrum to our knowledge for the first time.
2,134 citations
TL;DR: In this article, five massive gold-cluster molecules have been isolated in high yield and have undergone separate structural characterization, and their electronic structure has been deduced by optical absorption spectroscopy.
Abstract: Five massive gold-cluster molecules have been isolated in high yield and have undergone separate structural characterization, and their electronic structure has been deduced by optical absorption spectroscopy. These new molecules are distinguished by a crystalline (or quasicrystalline) core of densely packed Au atoms, ranging in size from ∼1.1 nm (∼40 atoms) to ∼1.9 nm (∼200 atoms), surrounded by a compact monolayer of various thio (RS) adsorbates. They are obtained as the thermally and environmentally stable products of the reductive decomposition of nonmetallic (−AuS(R)−) polymer in solution, are separated according to size by fractional crystallization or column chromatography, as monitored by high-mass spectrometry, and are characterized structurally by methods including X-ray diffraction (small and large angle), high-resolution electron microscopy, and scanning tunneling microscopy. The optical absorption spectra of dilute solutions of these molecules show size-dependent steplike structure with an on...
576 citations
TL;DR: The surface-enhanced infrared absorption (SEIRA) as mentioned in this paper is a surface analytical tool that is very useful for in situ studies of electrode/electrolyte interfaces.
Abstract: Molecules adsorbed on evaporated thin metal films exhibit enormously strong infrared absorption. The thin metal films that exhibit the surface-enhanced infrared absorption (SEIRA) consist of metal particles much smaller than the wavelength of light. Electric field associated with the incident infrared radiation is enhanced via the excitation of localized plasmon of the particles, yielding the absorption enhancement. Preferential orientation and the change in absorption coefficient of molecules caused by chemisorption onto the metal surface provide additional enhancement. Most characteristic observations in SEIRA experiments are well explained by a simple electromagnetic theory. The infrared spectroscopy utilizing the SEIRA effect is promising as a new surface analytical tool. In particular, it is very useful for in situ studies of electrode/electrolyte interfaces. By the combined use of the attenuated-total-reflection technique, reactions and adsorption/desorption of molecules at the interfaces can be inv...
568 citations
TL;DR: In this paper, the authors demonstrate that a commercial single-frequency cavity ring down spectroscopy (CRDS) can also be conveniently employed, allowing to gain in spectral resolution, signal intensity and data acquisition rate.
512 citations
TL;DR: Field measurements support the temperature and salinity dependencies found in the laboratory both in the near infrared and at shorter wavelengths.
Abstract: We have measured the absorption coefficient of pure and salt water at 15 wavelengths in the visible and near-infrared regions of the spectrum using WETLabs nine-wavelength absorption and attenuation meters and a three-wavelength absorption meter. The water temperature was varied between 15 and 30 degrees C, and the salinity was varied between 0 and 38 PSU to study the effects of these parameters on the absorption coefficient of liquid water. In the near-infrared portion of the spectrum the absorption coefficient of water was confirmed to be highly dependent on temperature. In the visible region the temperature dependence was found to be less than 0.001 m-1 degrees C except for a small region around 610 nm. The same results were found for the temperature dependence of a saltwater solution. After accounting for index-of-refraction effects, the salinity dependence at visible wavelengths is negligible. Salinity does appear to be important in determining the absorption coefficient of water in the near-infrared region. At 715 nm, for example, the salinity dependence was -0.00027 m-1 /PSU. Field measurements support the temperature and salinity dependencies found in the laboratory both in the near infrared and at shorter wavelengths. To make estimates of the temperature dependence in wavelength regions for which we did not make measurements we used a series of Gaussian curves that were fit to the absorption spectrum in the visible region of the spectrum. The spectral dependence on temperature was then estimated based on multiplying the Gaussians by a fitting factor.
470 citations
TL;DR: This review describes a relatively new direct absorption technique that is developed for measuring the electronic spectra of jet-cooled molecules and clusters with both high sensitivity and high spectral resolution.
Abstract: The measurement of electronic spectra of supersonically cooled molecules and clusters is a widely used approach for addressing many problems in chemistry. The most established techniques for making such measurements are laser-induced fluorescence (LIF) and resonance-enhanced multiphoton ionization (REMPI), and both have been employed very successfully in a large number of studies. However, both methods often fail for systems containing more than a few atoms, due to rapid internal conversion, predissociation, or other dynamical processes. Even for small systems, the vibronic band intensities are often contaminated by intramolecular relaxation dynamics; in such cases, these techniques cannot be used for reliable intensity measurements. For clusters that exhibit rapid photofragmentation, depletion spectroscopy can be employed quite effectively to measure their vibronic structure, but again, dynamic effects complicate the interpretation of spectra. The same considerations apply to other types of “action” spectroscopy. It would often be preferable to measure the electronic spectra of molecules and clusters in direct absorption, as this approach is the most straightforward and accurate means of determining absolute vibronic band intensities and for accessing states that are invisible to LIF or REMPI. The problem, of course, is that direct absorption methods are generally orders of magnitude less sensitive than the “action” techniques and are, therefore, difficult to apply to transient species, such as clusters or radicals. In this review, we describe a relatively new direct absorption technique that we have developed for measuring the electronic spectra of jet-cooled molecules and clusters with both high sensitivity and high spectral resolution. The method is based on measurement of the time rate of decay of a pulse of light trapped in a high reflectance optical cavity; we call it cavity ringdown laser absorption spectroscopy (CRLAS). In practice, pulsed laser light is injected into an optical cavity that is formed by a pair of highly reflective (R > 99.9%) mirrors. The small amount of light that is now trapped inside the cavity reflects back and forth between the two mirrors, with a small fraction (∼1 R) transmitting through each mirror with each pass. The resultant transmission of the circulating light is monitored at the output mirror as a function of time and allows the decay time of the cavity to be determined. A simple picture of the cavity decay event for the case where the laser pulse is temporally shorter than the cavity round trip transit time is presented in Figure 1. In this case, the intensity envelope of these discrete transmitted pulses exhibits a simple exponential decay. The time required for the cavity to decay to 1/e of the initial output pulse is called the “cavity ringdown” time. Determination of the ringdown time allows the absolute single pass transmission coefficient of the cavity to be determined with high accuracy, given the mirror spacing. The apparatus is converted to a sensitive absorption spectrometer simply by placing an absorbing medium between the two mirrors and recording the frequency dependent ringdown time of the cavity. Ideally, the ringdown time is a function of only the mirror reflectivities, cavity dimensions, and sample absorption. Absolute absorption intensities are obtained by subtracting the base-line transmission of the cavity, which is determined when the laser wavelength is off-resonance with all molecular transitions. † IBM Predoctoral Fellow. Current address: Sandia National Laboratories, M/S 9055, Livermore, CA 94551-0969. ‡ Los Gatos Research. 25 Chem. Rev. 1997, 97, 25−51
421 citations
TL;DR: In this paper, the spectroscopic behavior of colloidal InP quantum dots (QDs) has been investigated as a function of the mean QD diameter (which ranged from 26 to 60 A).
Abstract: The spectroscopic behavior of colloidal InP quantum dots (QDs) has been investigated as a function of the mean QD diameter (which ranged from 26 to 60 A). Absorption spectra show up to three peaks or shoulders which reflect excited state transitions in the QDs. Global photoluminescence (PL) spectra (excitation well to the blue of the absorption onset and which consequently excites most of the QDs in the size distribution) show broad PL emission. The emission and absorption features shift to higher energy with decreasing QD size. Resonant PL spectra (size-selective excitation into the tail of the absorption onset) show increasing fluorescence line narrowing with increasing excitation wavelength; PL and photoluminescence excitation spectroscopy were used to derive the PL red shift as a function of QD size. The resonant red shifts for QDs of a single size were extracted from PL data that reflect the emission from an ensemble of QD diameters. An analysis of the single-dot resonant red shift (difference betwee...
356 citations
TL;DR: In this paper, the authors report the control of interference in optical absorption by quantum mechanical tunnelling, which can provide a way to make semiconductor lasers operate without population inversion.
Abstract: The sign of the interference (constructive or destructive) between quantum-mechanical paths depends on the phase difference between the paths. In the Fano effect1 two optical paths from the ground state of a system — one direct and one mediated by a resonance — to a state in an energy continuum interfere to produce an asymmetric absorption spectrum that falls to zero near the absorption maximum. Zero absorption occurs as the wavelength is scanned across the resonance, at a photon energy corresponding to a 180 ° phase difference between the paths. Similar interference effects occur when two absorption paths are mediated by two different states, and they provide the basis for lasers that operate without a population inversion2,3,4,5,6,7. Here we report the control, by quantum mechanical tunnelling, of interference in optical absorption. The two intermediate states are resonances that arise from the mixing of the states in two adjacent semiconductors quantum wells, which are broadened by tunnelling into the same energy continuum through an ultra-thin potential-energy barrier. Inverting the direction of tunnelling by reversing the position of the barrier with respect to the two quantum wells changes the interference from destructive to constructive, as predicted theoretically. This effect might provide a way to make semiconductor lasers without population inversion8.
318 citations
TL;DR: In this paper, an elementary empirical model for the distribution of electronic states of an amorphous semiconductor is presented, and the functional form of the optical absorption spectrum is determined, focusing on the joint density of states function, which dominates the absorption spectrum over the range of photon energies.
Abstract: An elementary empirical model for the distribution of electronic states of an amorphous semiconductor is presented. Using this model, we determine the functional form of the optical absorption spectrum, focusing our analysis on the joint density of states function, which dominates the absorption spectrum over the range of photon energies we consider. Applying our optical absorption results, we then determine how the empirical measures commonly used to characterize the absorption edge of an amorphous semiconductor, such as the Tauc gap and the absorption tail breadth, are related to the parameters that characterize the underlying distribution of electronic states. We, thus, provide the experimentalist with a quantitative means of interpreting the physical significance of their optical absorption data.
300 citations
TL;DR: In this article, it is suggested that, at low copper ion concentrations, copper ions bound onto the surface of CdS nanoparticles exist as isolated Cu+ ions, which leads to formation of a new, red-shifted, luminescence band.
Abstract: Nonstoichiometric cadmium sulfide nanoparticles ([Cd2+]/[S2-] = 3) in 2-propanol were surface-modified with Cu2+ ions. Addition of copper(II) perchlorate to CdS nanoparticles leads to binding of copper ions onto the surface of the semiconductor, accompanied by rapid reduction of Cu2+ to Cu+, as confirmed by EPR and absorption spectra. Copper(II) perchlorate also quenches the recombination luminescence of CdS nanoparticles effectively. The quenching data obey a static interaction model, which confirms the binding of copper ions onto CdS. The latter was confirmed also by ultrafiltration and ICP spectroscopy. Copper ions bound onto the surface of CdS lead to formation of a new, red-shifted, luminescence band. The maximum of the new band is at 14 700 cm-1 compared to that of the original band at 17 900 cm-1. It is suggested that, at low copper ion concentrations, copper ions bound onto the surface of CdS nanoparticles exist as isolated Cu+ ions. They create a new energy level in the bandgap at about 1.2 eV be...
TL;DR: Aqueous dispersions of rod-like gold particles are obtained by electrodeposition in nanopores of anodized alumina attached to a conductive support followed by dissolution of the alumina and stabilization of the rods with poly(vinylpyrrolydon).
Abstract: Aqueous dispersions of rodlike gold particles are obtained by electrodeposition in nanopores of anodized alumina attached to a conductive support followed by dissolution of the alumina and stabilization of the rods with poly(vinylpyrrolydon). The obtained sol of monodisperse gold rods is examined by electron microscopy and visible (VIS) and near-infrared (NIR) spectroscopy. In the VIS/NIR absorption spectra two absorption maxima are present. With increasing aspect ratio, the maximum around 520 nm shifts to shorter wavelength, while the other maximum shifts into the near-infrared regime, which is in agreement with theoretical predictions.
TL;DR: In this paper, high-level optical properties of hexagonal (2H polytype) MoS2 and several isomorphous Mo and W chalcogenides have been synthesized with excellent control over cluster size.
Abstract: Highly crystalline nanoclusters of hexagonal (2H polytype) MoS2 and several of its isomorphous Mo and W chalcogenides have been synthesized with excellent control over cluster size down to ∼2 nm. These clusters exhibit highly structured, bandlike optical absorption and photoluminescence spectra which can be understood in terms of the band-structures for the bulk crystals. Key results of this work include: (1) strong quantum confinement effects with blue shifts in some of the absorption features relative to bulk crystals as large as 4 eV for clusters ∼2.5 nm in size, thereby allowing great tailorability of the optical properties; (2) the quasiparticle (or excitonic) nature of the optical response is preserved down to clusters ≲2.5 nm in size which are only two unit cells thick; (3) the demonstration of the strong influence of dimensionality on the magnitude of the quantum confinement. Specifically, three-dimensional confinement of the carriers produces energy shifts which are over an order of magnitude lar...
TL;DR: In this article, the authors observed a 50% reduction in absorption between the subband resonances which can be explained by taking into account the coherent coupling of the upper states, analogous to electromagnetically induced transparency (EIT) in atomic systems.
Abstract: We report the observation of tunneling induced transparency in asymmetric double quantum well structures. Resonant tunneling through a thin barrier is used to coherently couple the two upper states in a three level system of electronic subbands in a GaAs/AlGaAs structure. This creates Fano-type interferences for the collective intersubband excitations in the absorption from the ground state, analogous to electromagnetically induced transparency (EIT) in atomic systems. We observe a 50% reduction in absorption between the subband resonances which can be explained by taking into account the coherent coupling of the upper states. We analyze the bias dependent absorption spectra and determine the relevant lifetime broadening and dephasing rates for the transitions.
TL;DR: In this paper, the surface oxidation mechanisms of TiN and CrN films were studied by means of x-ray photoelectron (XPS) and absorption spectroscopy (XAS).
Abstract: Surface oxidation mechanisms of TiN and CrN films were studied by means of x-ray photoelectron (XPS) and absorption spectroscopy (XAS). In the N 1s XPS spectra of both the oxidized TiN and CrN films, a feature assigned to molecular nitrogen was observed in addition to a feature assigned to nitride. The assignment was confirmed by the N K-edge XAS spectra of the TiN and CrN films which exhibited a sharp feature at 401.4 eV. Besides these features, the N 1s XPS spectra of the oxidized TiN films showed a third feature, which was assigned to NX–Ti–OY like structures taking into account the change in the Ti 2p XPS spectra. However, no evident feature assigned to NX–Ti–OY like structures was observed in the XAS spectra because of the overlapping with the nitride features. The above results indicated that the CrN films directly changed to Cr2O3 with the formation of molecular nitrogen in the interstitial positions of the surface oxide layers, while the TiN films were oxidized to TiO2 through the formation of NX–...
TL;DR: In this paper, the authors used hydrodynamical simulations to investigate the spatial distribution and absorption properties of metal-enriched gas in such regions of ongoing galaxy formation, and observed column density ratios of different ionic species at z = 3 can be well reproduced if a mean metallicity [Z/H] = -2.5, relative abundances as found in metal-poor stars, a UV background with intensity J-22 = 3 at the Lyman limit, and either a power-law spectrum (J ∝ ν-1.5) or the
Abstract: In a hierarchical cosmogony, galaxies build up by continuous merging of smaller structures. At z = 3, the matter content of a typical present-day galaxy is dispersed over several individual clumps embedded in sheetlike structures, often aligned along filaments. We have used hydrodynamical simulations to investigate the spatial distribution and absorption properties of metal-enriched gas in such regions of ongoing galaxy formation. The metal and hydrogen absorption features produced by the collapsing structures closely resemble observed QSO absorption systems over a wide range in H I column density. Strong C II and Si IV absorption occurs for lines of sight passing the densest regions close to the center of the protogalactic clumps, while C IV is a good tracer of the prominent filamentary structures and O VI becomes the strongest absorption feature for lines of sight passing through low-density regions far away from fully collapsed objects. The observed column density ratios of the different ionic species at z = 3 can be well reproduced if a mean metallicity [Z/H] = -2.5, relative abundances as found in metal-poor stars, a UV background with intensity J-22 = 3 at the Lyman limit, and either a power-law spectrum (J ∝ ν-1.5) or the spectral shape proposed by Haardt & Madau are assumed. The observed scatter in [C/H] is about a magnitude larger than that in the simulations, which suggests an inhomogeneous metal distribution. Observed and simulated Doppler parameter distributions of H I and C IV absorption lines are in good agreement, which indicates that shock heating due to gravitational collapse is a second important heating agent in addition to photoionization heating. The large velocity spreads seen in some C IV systems may be due to the occasional alignments of the observer's line of sight with expanding large-scale filaments. Both high-ionization multicomponent heavy-element absorbers and damped Lyα systems can arise from groups of moderately sized protogalactic clumps (Mbaryon ~ 109 M☉). Recent detections of star-forming galaxies at similar redshifts are consistent with this picture.
TL;DR: In this paper, the authors used ringdown laser absorption spectroscopy (IR-CRLAS) to determine the absolute concentrations of water dimers, trimers, tetramers, and pentamers in a pulsed supersonic expansion for the first time.
Abstract: The recently developed technique of infrared cavity ringdown laser absorption spectroscopy (IR-CRLAS) has been employed in the 3.0 μm region to determine the absolute concentrations of water dimers, trimers, tetramers, and pentamers in a pulsed supersonic expansion for the first time. Additional spectral features are reported, one of which we assign to the bound O−H stretching bands of the hexamer. Additionally, by simple variation of the jet stagnation pressure, the collective O−H stretching absorption from all clusters produced in the expansion was observed to change from that of discrete features of small clusters to band profiles of liquid water and finally to amorphous ice.
TL;DR: In this article, a new software package particularly adapted to the demands of energy-dispersive XAS (DXAS) and time resolved XAS experiments is introduced, called WinXAS.
Abstract: A new software package particularly adapted to the demands of energy-dispersive XAS (DXAS) and time resolved XAS experiments is introduced. Owing to the dispersive set-up and the employed measuring procedure, treatment of dispersive XAS data requires a series of additional steps compared to conventional XAS data reduction. WinXAS is running under MS-WINDOWS® and contains some unique features in terms of a user friendly graphical environment, energy calibration of dispersive XAS data and the capabilities to process a large number of consecutive absorption spectra. Since the number of absorption spectra measured during a single time-resolved experiment can amount to several hundreds, WinXAS allows to record single data reduction steps and to apply the obtained series on each absorption spectrun of one experiment. Additionally, WinXAS contains a large number of numerical functions, including conventional XAS data reduction including a complete FEFF [5] interface, smoothing, glitch removal, least-squares refinement, etc.
TL;DR: In this paper, the C 1s and O 1s X-ray absorption spectra of poly(ethylene terephthalate) (PET) have been recorded using transmission, fluorescence, and electron yield detection.
Abstract: The C 1s and O 1s X-ray absorption spectra of poly(ethylene terephthalate) (PET) have been recorded using transmission, fluorescence, and electron yield detection. The corresponding electron energy loss spectra (EELS) have been recorded in a scanning transmission electron microscope. These results are compared to the C 1s and O 1s spectra of gas phase 1,4-dimethyl terephthalate (the monomer of PET) recorded using EELS. The comparison of monomer and polymer materials in different phases and with different techniques has aided the understanding of the relative strengths and limitations of each technique as well as assisting the spectral interpretation. Good agreement is found in the overall shape and the energies of the spectral features. Relatively minor differences in intensities can be understood in terms of the properties of the individual spectroscopic techniques. The critical dose for radiation damage by 100 keV electrons incident on PET at 100 K is found to be (1.45 ± 0.15) × 103 eV nm-3. In contrast...
TL;DR: The absorption spectrum of the purest available water is measured with photothermal deflection spectroscopy and shows an absorption minimum in the blue region of the spectrum that is deeper than in most previously documented pure-water absorption studies.
Abstract: We measured the absorption spectrum (340-640 nm) of the purest available water with photothermal deflection spectroscopy. Our spectrum exhibits an absorption minimum in the blue region of the spectrum that is deeper than in most previously documented pure-water absorption studies. We attribute this to exceptional sample purity and our technique's inherent freedom from scattering effects. Because the absorption minimum is significantly lower, our spectrum displays high-order molecular resonance structure not observed in any previous absorption studies to our knowledge. We find the minimum in the absorption spectrum of pure water is 0.0062 ? 0.0006 m(-1) at 420 nm and 25 degrees C.
TL;DR: Thin oxide films (from one to tens of monolayers) of SiO2, MgO, NiO, Al2O3, FexOy, and TiO2 supported on refractory metal substrates have been prepared by depositing the oxide metal precursor in a background of oxygen.
Abstract: Thin oxide films (from one to tens of monolayers) of SiO2, MgO, NiO, Al2O3, FexOy, and TiO2 supported on refractory metal substrates have been prepared by depositing the oxide metal precursor in a background of oxygen (ca 1 x 10(-5) Torr). The thinness of these oxide samples facilitates investigation by an array of surface techniques, many of which are precluded when applied to the corresponding bulk oxide. Layered and mixed binary oxides have been prepared by sequential synthesis of dissimilar oxide layers or co-deposition of two different oxides. Recent work has shown that the underlying oxide substrate can markedly influence the electronic and chemical properties of the overlayer oxide. The structural, electronic, and chemical properties of these ultrathin oxide films have been probed using Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), electron energy loss spectroscopy (ELS), ion-scattering spectroscopy (ISS), high-resolution electron energy loss spectroscopy (HREELS), infrared reflectance absorption spectroscopy (IRAS), temperature-programmed desorption (TPD), scanning tunneling microscopy (STM), and scanning tunneling spectroscopy (STS).
TL;DR: In this paper, three-pulse echo peak shift measurements were performed on the B875 and B850 bands of detergent-isolated LH1 and LH2 complexes at room temperature.
Abstract: Three-pulse echo peak shift measurements were performed on the B875 and B850 bands of detergent-isolated LH1 and LH2 complexes at room temperature. The peak shifts are much larger and decay much faster than typically observed for dye molecules in solution. Simulations of the peak shifts based on the optical transition frequency correlation function, M(t), are presented. M(t) includes contributions from rapid protein fluctuations, vibrational motion, and energy transfer. The model reproduces the room temperature absorption spectra of B850 and B875, shows that the coupling of electronic and nuclear degrees of freedom is much weaker than for dyes in solution, and identifies contributions to the line shapes that may be important to the energy transfer processes. The implications of these results for the extent of electronic delocalization in LH1 and LH2 are also discussed. Although the role of coherence transfer still needs to be understood, the results are shown to be consistent with the use of weak-coupling excitation transfer models of B850 and B875.
TL;DR: In this paper, an analysis of the IRRAS intensities of the methylene and carbonyl stretching vibrations reveals that, of the limited set of chain tilt angles possible with respect to the surface normal, a chain tilt angle of 0° provides by far the best fit to the data.
Abstract: Monolayers of behenic acid methyl ester at the air/H2O and air/D2O interfaces provide a convenient test for quantitative analysis of infrared reflection−absorption spectroscopy (IRRAS) intensities. Spectra were acquired for both s- and p-polarized radiation at angles of incidence of 35°, 40°, 45°, and 50°. The observed ∼10 cm-1 splitting (at a surface pressure of 14 mN/m) for both the methylene scissoring and rocking modes provides direct evidence for the occurrence of a perpendicular orthorhombic subcell structure and for the existence of all-trans acyl chains. Analysis of the IRRAS intensities of the methylene and carbonyl stretching vibrations reveals that, of the limited set of chain tilt angles possible with respect to the surface normal, a chain tilt angle of 0° provides by far the best fit to the data. For each vibration, data for both polarizations at all four angles were fit with a single set of three parameters: chain tilt angle, effective extinction coefficient (kmax), and the overall degree o...
TL;DR: In this article, the back electron transfer between the photoinjected electron and the oxidized sensitizer plays an important role in controlling the efficiency of net electron transfer, and it is shown that most of the transfer is multiexponential and most is completed within a few hundred nanoseconds.
Abstract: Adsorption of a cationic dye, cresyl violet, on SnO2 and SiO2 nanoclusters and nanocrystalline thin films results in the formation of H-aggregates. These dyes are photochemically and electrochemically active and extend the photoresponse of large bandgap semiconductors such as SnO2. Photocurrent generation in dye capped nanocrystalline films of SnO2 has been demonstrated with visible light excitation. A photon-to-photocurrent generation efficiency around 1% has been observed at 510 nm. Back electron transfer between the photoinjected electron and the oxidized sensitizer plays an important role in controlling the efficiency of net electron transfer. Transient absorption and microwave absorption measurements of the dye aggregate capped SnO2 films suggest that the back electron transfer is multiexponential and most is completed within a few hundred nanoseconds. The activation energy of the back electron transfer process is very low (∼1.7 kJ/mol).
TL;DR: In this article, the authors presented results from Keck I high-resolution spectroscopy of the radio loud quasar PKS 0123+257 (PKS 01 23+257) at a redshift of 2.369 and showed that the absorption lines are positioned near the centers of the broad emission lines.
Abstract: We present results from Keck I high resolution spectroscopy of the radio loud quasar PKS 0123+257 ($z_e$=2.364, V=17.5). In this object we detect Ly$\alpha$, N V 1238,1242, Si IV 1393,1402, and C IV 1548,1550 in an absorption system at a redshift of 2.369. The Ly$\alpha$ line has a square- bottomed profile suggesting a high column density of gas, yet the line does not reach zero intensity. The resolved C IV doublet ratio also clearly demonstrates that the absorbing clouds at this redshift do not fully occult the background light source along our line-of-sight.
The absorption lines are positioned near the centers of the broad emission- lines and the coverage fraction of the strongest absorption lines varies inversely proportionally with the strength of the corresponding emission lines. This implies that although the absorption-line region may obscure the continuum source, it does not completely occult the broad emission-line region. This effect suggests that the lines are formed close to the QSO central region. A model is proposed in which the apparent coverage fraction derived for the weaker absorption lines may vary with the column density of the lines.
Broad absorption-lines (which are known to be intrinsic) are found nearly exclusively in radio-quiet objects. Intrinsic narrow absorption lines have previously been found in radio quiet QSOs; it is therefore significant that an intrinsic absorption system has been verified in a radio loud quasar.
TL;DR: A Liquid Core Waveguide (LCW) can be used to extend the sensitivity of conventional absorbance spectroscopy by two or more orders of magnitude as discussed by the authors, and it has been shown that a 4.47m pathlength LCW made of Teflon AF-2400 provides a 0.2nmol−dm−3 detection limit and a linear response between 0.5 and 10nmol −m−m−3.
TL;DR: In this article, the authors used the shielding effect of the dendrimer branches on the Ru-bipyridine core, which limits the quenching effect of molecular oxygen.
Abstract: Several synthetic strategies have been explored to prepare dendrimers having the [Ru(bpy)3]2+ complex as their core (bpy = 2,2′-bipyridine). Dendritic ligands have been synthesized by attaching branches in the 4,4′-positions of bpy. The largest dendritic bipyridine ligand contains 54 peripherical methylester units. Four RuII dendritic complexes have been prepared. Their absorption and emission spectra are very similar to those of the unsubstituted parent RuII–bipyridine complexes. The large dendritic complexes, however, exhibit a more intense emission and a longer excited-state lifetime than [Ru(bpy)3]2+ in aerated solutions. This is due to the shielding effect of the dendrimer branches on the Ru–bipyridine core, which limits the quenching effect of molecular oxygen. For the largest dendritic complex, which contains 54 peripherical methylester units, the excited-state lifetime in aerated acetonitrile solution is longer than 1 μs, and the rate constant for dioxygen quenching is twelve times smaller than for [Ru(bpy)3]2+.
TL;DR: Species concentrations above a laminar, premixed, methane-air flame were determined from measured absorption in a fast-flow multipass absorption cell containing probe-sampled combustion gases; good agreement was found with calculated chemical equilibrium values.
Abstract: A diode laser sensor has been applied to monitor CO, CO(2), and CH(4) in combustion gases with absorption spectroscopy and fast extraction-sampling techniques. Survey spectra of the CO 3nu band (R branch) and the 2nu(1) + 2nu(2)(0) + nu(3) CO(2) band (R branch) near 6350 cm(-1) and H(2)O lines from the nu(1) + 2nu(2) and 2nu(2) + nu(3) bands in the spectral region from 6345 to 6660 cm(-1) were recorded and compared with calculated spectra (from the HITRAN 96 database) to select optimum transitions for species detection. Species concentrations above a laminar, premixed, methane-air flame were determined from measured absorption in a fast-flow multipass absorption cell containing probe-sampled combustion gases; good agreement was found with calculated chemical equilibrium values.
TL;DR: In this article, the binding environments of Cu and Pb complexed by soil humic substances using synchrotron-based X-ray absorption spectroscopy were investigated with the assistance of bond network analysis.