Time-dependent density-functional calculations for optical spectra of Na-2 and Na-4 clusters

With the frame of the time-dependent local density approximation, an efficient description of the optical response of clusters has been used to study the photo-absorption cross section of Na-2 and Na-4 clusters. It is shown that our calculated results are in good agreement with the experiment. In addition, our calculated spectrum for the Na-4 cluster is in better agreement with experiment than the GW absorption spectrum.

Growth and vibrational spectra of doped KMgF3 single crystal

The different ions doped KMgF3 single crystals are prepared by the vertical Bridgman method. The near-infrared absorption spectra for different parts of all as-growth crystals indicate that there is the best transparency in middle part. The correlation between the vibronic frequencies of Eu2+ and the site displacement of Cu+ co-doped ions is firstly studied, which indicates that Cu+ ions replace the site of the Mg2+ ions. The co-doped Eu2+ counteracts the charge misfit causing by the replacement of Mg2+ with Cu+. The overlapping of the emission spectra of the Eu2+ and the excitation spectra of the Cu+ results in the energy transfer from Eu2+ to Cu+.

Studies on the coordination of Pr(III) with adrenaline by potentiometry and absorption spectroscopy

The stability constant for complex of Pr(III) with adrenaline has been determined by potentiometric titration under biological conditions (37 degrees C and 0.15 mol/L NaCl). The absorption spectra of the Pr(III)-adrenaline system exhibit characteristic bands of Pr(III) at lower pH values. However, the charge transfer band which is due to the coordination of Pr(III) with adrenaline has been observed at higher pH values.

Locating hexagonal and cubic phases in boron nitride using wavelength-selective optically detected x-ray absorption spectroscopy

Locating hexagonal and cubic phases in boron nitride using wavelength-selective optically detected x-ray absorption spectroscopy, D.A. Evans, A.R. Vearey-Roberts, N.R.J. Poolton Appl Phys Lett 89, (2006) 161107

Broadband optical cavity absorption spectroscopy in the near-ultraviolet: applications in atmospheric chemistry

A novel spectroscopic method, incoherent broadband cavity enhanced absorption spectroscopy (IBBCEAS), has been modified and extended to measure absorption spectra in the near-ultraviolet with high sensitivity. The near-ultraviolet region extends from 300 to 400 nm and is particularly important in tropospheric photochemistry; absorption of near-UV light can also be exploited for sensitive trace gas measurements of several key atmospheric constituents. In this work, several IBBCEAS instruments were developed to record reference spectra and to measure trace gas concentrations in the laboratory and field. An IBBCEAS instrument was coupled to a flow cell for measuring very weak absorption spectra between 335 and 375 nm. The instrument was validated against the literature absorption spectrum of SO2. Using the instrument, we report new absorption cross-sections of O3, acetone, 2-butanone, and 2-pentanone in this spectral region, where literature data diverge considerably owing to the extremely weak absorption. The instrument was also applied to quantifying low concentrations of the short-lived radical, BrO, in the presence of strong absorption by Br2 and O3. A different IBBCEAS system was adapted to a 4 m3 atmosphere simulation chamber to record the absorption cross-sections of several low vapour pressure compounds, which are otherwise difficult to measure. Absorption cross-sections of benzaldehyde and the more volatile alkyl nitrites agree well with previous spectra; on this basis, the cross-sections of several nitrophenols are reported for the first time. In addition, the instrument was also used to study the optical properties of secondary organic aerosol formed following the photooxidation of isoprene. An extractive IBBCEAS instrument was developed for detecting HONO and NO2 and had a sensitivity of about 10-9 cm-1. This instrument participated in a major international intercomparison of HONO and NO2 measurements held in the EUPHORE simulation chamber in Valencia, Spain, and results from that campaign are also reported here.

Predicting the frequency dispersion of electronic hyperpolarizabilities on the basis of absorption data and thomas-kuhn sum rules

Successfully predicting the frequency dispersion of electronic hyperpolarizabilities is an unresolved challenge in materials science and electronic structure theory. We show that the generalized Thomas-Kuhn sum rules, combined with linear absorption data and measured hyperpolarizability at one or two frequencies, may be used to predict the entire frequency-dependent electronic hyperpolarizability spectrum. This treatment includes two- and three-level contributions that arise from the lowest two or three excited electronic state manifolds, enabling us to describe the unusual observed frequency dispersion of the dynamic hyperpolarizability in high oscillator strength M-PZn chromophores, where (porphinato)zinc(II) (PZn) and metal(II)polypyridyl (M) units are connected via an ethyne unit that aligns the high oscillator strength transition dipoles of these components in a head-to-tail arrangement. We show that some of these structures can possess very similar linear absorption spectra yet manifest dramatically different frequency dependent hyperpolarizabilities, because of three-level contributions that result from excited state-to excited state transition dipoles among charge polarized states. Importantly, this approach provides a quantitative scheme to use linear optical absorption spectra and very limited individual hyperpolarizability measurements to predict the entire frequency-dependent nonlinear optical response. Copyright © 2010 American Chemical Society.

Nonharmonic transverse vibration of the H-bonded molecules and the THz spectra in ice and water

A nonlinear equation of motion is found for the dimer comprising two charged H2O molecules. The THz dielectric response to nonharmonic vibration of a nonrigid dipole, forming the hydrogen bond (HB), is found in the direction transverse to this bond. An explicit expression is derived for the autocorrelator that governs the spectrum generated by transverse vibration (TV) of such a dipole. This expression is obtained by analytical solution of the truncated set of recurrence equations. The far infrared (FIR) spectra of ice at the temperature - 7 degrees C are calculated. The wideband, in the wavenumber (frequency) v range 0... 100.0 cm(-1), spectra are obtained for liquid water at room temperature and for supercooled water at -5.6 degrees C. All spectra are represented in terms of the complex permittivity epsilon(v) and the absorption coefficient alpha(v). The obtained analytical formula for epsilon comprises the term epsilon(perpendicular to) pertinent to the studied TV mechanism with three additional terms Delta epsilon(q), Delta epsilon(mu), and epsilon(or) arising, respectively, from: elastic harmonic vibration of charged molecules along the H-bond; elastic reorientation of HB permanent dipoles; and rather free libration of permanent dipoles in 'defects' of water/ice structure. The suggested TV-dielectric relaxation mechanism allows us: (a) to remove the THz 'deficit' of loss epsilon" inherent in previous theoretical studies; (b) to explain the THz loss and absorption spectra in supercooled (SC) water; and (c) to describe, in agreement with the experiment, the low- and high-frequency tails of the two bands of ice H2O located in the range 10...300 cm(-1). Specific THz dielectric properties of SC water are ascribed to association of water molecules, revealed in our study by transverse vibration of HB charged molecules. (C) 2006 Published by Elsevier B.V.

The electronic spectra and the determination of the excited state geometry of 3A" propynal /|nby Chhiu-Tsu Lin. -- 260 St. Catharines, Ont. : [s. n.],

Impurity free eluission spectra of HCCCHO and DCCCHO have been rephotographed using the electronic-energy-exchange method with benzene as a carrier gas. The near ultraviolet spectra of ReeCHO and DCCCHO were photographed in a sorption under conditions of high resolution with absorption path lengths up to 100 meters. The emission and absorption spectra of Propynal resulting from 3 n 1 t 1\ - A excitation has been reanalyzed in som.e detail. Botrl of the eH out-of-plane wagging modes were found to have negative anharmonicity. A barrier height of 56.8/0.0 cm- 1 and a nonplanar oft , , equilibrium angle of 17 3 /30 are calculated for the V 10/ lJ 11 modes. The in-plane and out-of-plane v1. brational modes in the 3A." and 1a~. ' elec ronic states of Propynal were subjected to a normal coordinate treatment in the approximat :on of tIle Urey-Bradley force field. From the relative oscillator strengths of the trans1·t1·0ns connect i ng t he v ibrat1•0n1ess lA' , state and t,he V1· bron1·C 3· if levels of the A state, the differences in equilibrium configuration were evaluated from an approximate Franck-Condon analysis based on the ground state normal coordinates. As this treatment gave 512 possible geometrical structures for the upper state, it 4 was necessary to resort to a comparison of the observed and calculated moments of inertia along with chemical intuition to isolate the structure. A test of the correctness of the calculated structure change and the vibrational assignment was raade by evaluating the intensities of the inplane and out-oi-plane fundarnental, sequence, and cross sequellce transitions y the exact Franck-Condon method.

Optical absorption studies of free (H2Pc) and rare earth (RePc) phthalocyanine doped borate glasses

Optical absorption studies of free base and rare earth incorporated phthalocyanine doped borate glass matrix are reported for the first lime. The absorption spectra recorded in the UV- VIS region show two well defined absorption bands of phthalocyanine (Pc) molecule, namely the Soret band (B) and the Q band. The Q band always shows its characteristic splitting in all the doped glass matrices and the intensities of these components are found to vary from one Pc to another. Some of the important optical parameters, namely optical absorption coefficient (a), molar extinction coefficient (ε), absorption cross section (σa), oscillator strength (f), electric dipole strength (q2), absorption half bandwidth (Δλ) of the principal optical transitions have also been evaluated. Moreover, the spectral dependence of refractive index (n) and thereby the optical dielectric constant (ε) on wavelength yielded values of carrier concentration to effective mass ratio (N/m*) of the phthalocyanine molecule in the present glassy systems. Optical band gap (Eg) and width of the band tail (Et) are computed and their variations among the prepared samples are also discussed.

Photoacoustic detection of two photon absorption in formaldehyde using pulsed dye laser

Absorption spectra of formaldehyde molecule in the gas phase have been recorded using photoacoustic (PA) technique with pulsed dye laser at various power levels. The spectral profiles at higher power levels are found to be different from that obtained at lower laser powers. Two photon absorption (TPA) is found to be responsible for the photoacoustic signal at higher laser power while the absorption at lower laser power level is attributed to one photon absorption (OPA) process. Probable assignments for the different transitions are given in this paper.

Higher oxides of chlorine: absorption cross-sections of Cl2O6 and Cl2O4, the decomposition of Cl2O6, and the reactions of OClO with O and O-3

The absorption cross-sections of Cl2O6 and Cl2O4 have been obtained using a fast flow reactor with a diode array spectrometer (DAS) detection system. The absorption cross-sections at the wavelengths of maximum absorption (lambda(max)) determined in this study are those of Cl2O6: (1.47 +/- 0.15) x 10(-17) cm(2) molecule(-1), at lambda(max) = 276 nm and T = 298 K; and Cl2O4: (9.0 +/- 2.0) x 10(-19) cm(2) molecule(-1), at lambda(max) = 234 nm and T = 298 K. Errors quoted are two standard deviations together with estimates of the systematic error. The shapes of the absorption spectra were obtained over the wavelength range 200-450 nm for Cl2O6 and 200-350 nm for Cl2O4, and were normalized to the absolute cross-sections obtained at lambda(max) for each oxide, and are presented at 1 nm intervals. These data are discussed in relation to previous measurements. The reaction of O with OCIO has been investigated with the objective of observing transient spectroscopic absorptions. A transient absorption was seen, and the possibility is explored of identifying the species with the elusive sym-ClO3 or ClO4, both of which have been characterized in matrices, but not in the gas-phase. The photolysis of OCIO was also re-examined, with emphasis being placed on the products of reaction. UV absorptions attributable to one of the isomers of the ClO dimer, chloryl chloride (ClClO2) were observed; some Cl2O4 was also found at long photolysis times, when much of the ClClO2 had itself been photolysed. We suggest that reports of Cl2O6 formation in previous studies could be a consequence of a mistaken identification. At low temperatures, the photolysis of OCIO leads to the formation of Cl2O3 as a result of the addition of the ClO primary product to OCIO. ClClO2 also appears to be one product of the reaction between O-3 and OCIO, especially when the reaction occurs under explosive conditions. We studied the kinetics of the non-explosive process using a stopped-flow technique, and suggest a value for the room-temperature rate coefficient of (4.6 +/- 0.9) x 10(-19) cm(3) molecule(-1) s(-1) (limit quoted is 2sigma random errors). The photochemical and thermal decomposition of Cl2O6 is described in this paper. For photolysis at k = 254 nm, the removal of Cl2O6 is not accompanied by the build up of any other strong absorber. The implications of the results are either that the photolysis of Cl2O6 produces Cl-2 directly, or that the initial photofragments are converted rapidly to Cl-2. In the thermal decomposition of Cl2O6, Cl2O4 was shown to be a product of reaction, although not necessarily the major one. The kinetics of decomposition were investigated using the stopped-flow technique. At relatively high [OCIO] present in the system, the decay kinetics obeyed a first-order law, with a limiting first-order rate coefficient of 0.002 s(-1). (C) 2004 Elsevier B.V. All rights reserved.

Thermoluminescence and optical absorption studies of natural grossular minerals

The optical absorption spectra of two samples of grossular have been measured at room temperature. An intense charge transfer band (UVCT) of iron extends to the visible and near infrared region. Some peaks associated to Fe3+ ions in tetrahedral and octahedral positions have been identified and their energy levels were computed. Mn2+ and Fe2+ ions are responsible with some bands and probably these ions occupy dodecahedral positions. No change in the intensity of optical absorption spectra were found after gamma dose, but only the 505 nm band decreases with irradiation. The OH spectra, consisting of OH overtones at 2750nm and asymmetric OH bands in the near infrared region were observed in the two samples. The heat treatment produces Fe2+ -> Fe3+ and Mn2+ -> Mn3+ by oxidation. This last was observed in sample II only. The thermally stimulated luminescence of both grossular samples has been investigated. Due to differences in iron and manganese concentration, not only a large difference has been observed in their optical absorption behavior, but also a striking difference in their thermoluminescent behavior. Actually, it is not clear whether other impurities such as Ti, Na and K that are present in quite different concentration in grossular I and II are also contributing to the thermoluminescenct properties of both samples. (C) 2008 Elsevier Ltd. All rights reserved.

Two-photon absorption properties of a novel class of triarylamine compounds

Two-photon absorption spectra of a triarylamine compounds dissolved in toluene were measured using the well-known Z-scan technique, employing 120-fs laser pulse-width. According to the results, an extra band located at around 900 nm was observed only for triarylamine with azoaromatic units. On the other hand, a shift in the two-photon absorption band for triarylamine, with and without azoaromatic units, is observed when different electron donor/acceptors groups are changed. The fitting of the spectra, using sum-over-states model, allowed us to obtain the spectroscopic parameters of each molecule, which appears to be in reasonable agreement with molecules presenting similar structural moieties. (C) 2010 Elsevier B.V. All rights reserved.

Light emission and excitonic effect of boron nitride nanotubes observed by photoluminescent spectra

Photoluminescent (PL) and optical absorption spectra of high-yield multi-wall BN nanotubes (BNNTs) were systematically investigated at room temperature in comparison with commercial hexagonal BN (h-BN) powder. The direct band gap of the BNNTs was determined to be 5.75 eV, just slightly narrower than that of h-BN powder (5.82 eV). Two Frenkel excitons with the binding energy of 1.27 and 1.35 eV were also determined. However, they were not a distinctive characteristic of the BNNTs as reported previously. Observed broad UV–visible–NIR light emission demonstrates the potential of the BNNTs as a nano light source.