X-ray and ultraviolet photoelectron spectroscopy studies of the interaction of carbon monoxide with oxygen adsorbed on silver covered with potassium, caesium or barium

X-ray and He(II) ultraviolet photoelectron spectroscopy studies of the interaction of CO with oxygen on potassium-, caesium- and barium-covered Ag surfaces have shown the formation of carbonate at 300 K. While on a caesium-covered surface only carbonate formation takes place, on the potassium- and barium-covered surfaces molecularly chemisorbed CO is also formed. The variation of the surface concentrations of carbon and oxygen with temperature has been examined and a reaction sequence for the interaction of CO with adsorbed oxygen on potassium-, caesium- and barium-covered Ag surfaces is suggested.

Ultraviolet radiation effects on fruit surface respiration and chlorophyll fluorescence

High-value fruit crops are exposed to a range of environmental conditions that can reduce fruit quality. Solar injury (SI) or sunburn is a common disorder in tropical, sub-tropical, and temperate climates and is related to: 1) high fruit surface temperature; 2) high visible light intensity; and, 3) ultraviolet radiation (UV). Positional changes in fruit that are caused by increased weight or abrupt changes that result from summer pruning, limb breakage, or other damage to the canopy can expose fruit to high solar radiation levels, increased fruit surface temperatures, and increased UV exposure that are higher than the conditions to which they are adapted. In our studies, we examined the effects of high fruit surface temperature, saturating photosynthetically-active radiation (PAR), and short-term UV exposure on chlorophyll fluorescence, respiration, and photosynthesis of fruit peel tissues from tropical and temperate fruit in a simulation of these acute environmental changes. All tropical fruits (citrus, macadamia, avocado, pineapple, and custard apple) and the apple cultivars 'Gala', 'Gold Rush', and 'Granny Smith' increased dark respiration (A0) when exposed to UV, suggesting that UV repair mechanisms were induced. The maximum quantum efficiency of photosystem II (Fv/Fm) and the quantum efficiency of photosystem II (ΦII) were unaffected, indicating no adverse effects on photosystem II (PSII). In contrast, 'Braeburn' apple had a reduced Fv/Fm with no increase in A0 on all sampling dates. There was a consistent pattern in all studies. When Fv/Fm was unaffected by UV treatment, A0 increased significantly. Conversely, when Fv/Fm was reduced by UV treatment, then A0 was unaffected. The pattern suggests that when UV repair mechanisms are effective, PSII is adequately protected, and that this protection occurs at the cost of higher respiration. However, when the UV repair mechanisms are ineffective, not only is PSII damaged, but there is additional short-term damage to the repair mechanisms, indicated by a lack of respiration to provide energy.

An ultraviolet photoelectron spectroscopic study of the electron states of iodine complexes with electron donors

HeI photoelectron spectra of the vapour phase complexes of diethylether and diethylsulphide with iodine have been investigated for the first time. The iodine orbital ionization energy decreases on complexation while the donor lone-pair orbital ionization energy increases markedly; the shifts are considerably larger in the sulphide complex as expected on the basis of enthalpy considerations.

Crystal Structure, Ultraviolet Spectrum, and Electronic Structure of a Strongly Twisted Push-Pull Ethylene, approaching an Amidinium-Vinylogous Dithioate Zwitterion

The crystal structure of 1,3-di benzyl -2 - (4,4-dimet hyl- 2,5- bist hioxocyclo hexylidene) imidazolidine (2) shows a twist of 80.8(5)' about the inter-ring bond, which has a length of 1.482(6) A. The near orthogonality of the donor and acceptor parts of this formal push-pull ethylene makes the structure approach that of a zwitterion, as evidenced by bond lengths indicating strong electron delocalization. The acceptor part approaches a vinylogous dithioate structure, the donor part an amidinium system. The U.V. spectrum shows an n + R and a R + R transition, at 51 1 and 41 7.5 nm, respectively; according to CNDO/S calculations these are located entirely in the [S-C-C-C-SI- part. Two bands at shorter wavelength are ascribed to transitions from combinations of the lone-pair orbitals on the sulphur atoms to a n* orbital in the [N-C-N] + part; this is facilitated by the near perpendicularity of the two parts of the molecule.

Adsorption of carbon monoxide on the surfaces of polycrystalline transition metals and alloys: electron energy loss and ultraviolet photoelectron spectral studies1

Adsorption of CO has been investigated on the surfaces of polycrystalline transition metals as well as alloys by employing electron energy loss spectroscopy (eels) and ultraviolet photoelectron spectroscopy (ups). CO adsorbs on polycrystalline transition metal surfaces with a multiplicity of sites, each being associated with a characteristic CO stretching frequency; the relative intensities vary with temperature as well as coverage. Whilst at low temperatures (80- 120 K), low coordination sites are stabilized, the higher coordination sites are stabilized at higher temperatures (270-300 K). Adsorption on surfaces of polycrystalline alloys gives characteristic stretching frequencies due to the constituent metal sites. Alloying, however, causes a shift in the stretching frequencies, indicating the effect of the band structure on the nature of adsorption. The up spectra provide confirmatory evidence for the existence of separate metal sites in the alloys as well as for the high-temperature and low-temperature phases of adsorbed CO.

Synthesis of wurtzite-phase ZnS nanocrystal and its optical properties

The wurtzite phase of ZnS nanocrystal has been prepared by annealing in 200-600 degrees C temperature range, its cubic phase of 2-3 nm size. prepared through soft chemical method. Results of isochronal experiments of 2 h at different temperatures indicate that visible transformation to wurtzite from cubic ZnS appears at a temperature of 400 degrees C, which is about three times smaller than that of bulk ZnS phase transition temperature. The phases, nanostructures, and optical absorption characteristics are obtained through X-ray diffraction. transmission electron microscopy, and UV-visible absorption spectroscopy. A stable and green photoluminescence emission peaked at 518 nm is observed from the 600 degrees C annealed samples, under ultraviolet light excitation.

Season of birth and location of residence: Defining the role of ultraviolet radiation exposure on childhood temperament and behaviour

This thesis added new insight to research knowledge about the role that season and ultraviolet radiation (UV) exposure during pregnancy has on children's temperament and behaviours, using a nation-wide longitudinal study. It was found that young children born in summer months are likely to have problematic behaviours. The thesis also found that summer-born children are likely to receive lowest levels of UV exposure during the gestational period. Finally, this work showed that low gestational UV exposure is associated with an increased risk of behavioural problems in children.

Enhanced catharanthine and vindoline production in suspension cultures of Catharanthus roseus by ultraviolet-B light

Suspension cultures of Catharanthus roseus were used to evaluate ultraviolet-B (UV-B) treatment as an abiotic elicitor of secondary metabolites. A dispersed cell suspension culture from C. roseus leaves in late exponential phase and stationary phase were irradiated with UV-B for 5 min. The stationary phase cultures were more responsive to UV-B irradiation than late exponential phase cultures. Catharanthine and vindoline increased 3-fold and 12-fold, respectively, on treatment with a 5-min UV-B irradiation.

Vacuum ultraviolet/atomic oxygen erosion resistance of amorphous Si0.26C0.43N0.31 coating

An amorphous silicon carbonitride (Si1-x-yCxN y, x = 0:43, y = 0:31) coating was deposited on polyimide substrate using the magnetron-sputtering method. Exposure tests of the coated polyimide in atomic oxygen beam and vacuum ultraviolet radiation were performed in a ground-based simulator. Erosion kinetics measurements indicated that the erosion yield of the Si0.26C0.43N0.31 coating was about 1.5x and 1.8 × 10-26 cm3 /atom during exposure in single atomic oxygen beam, simultaneous atomic oxygen beam, and vacuum ultraviolet radiation, respectively. These values were 2 orders of magnitude lower than that of bare polyimide substrate. Scanning electron and atomic force microscopy, X-ray photoelectron spectrometer, and Fourier transformed infrared spectroscopy investigation indicated that during exposures, an oxide-rich layer composed of SiO2 and minor Si-C-O formed on the surface of the Si 0.26C0.43N0.31 coating, which was the main reason for the excellent resistance to the attacks of atomic oxygen. Moreover, vacuum ultraviolet radiation could promote the breakage of chemical bonds with low binding energy, such as C-N, C = N, and C-C, and enhance atomic oxygen erosion rate slightly.

Spectroscopic investigations and luminescence spectra of Nd3+ and Dy3+ doped different phosphate glasses

Spectral properties of Nd3+ and Dy3+ ions in different phosphate glasses were studied and several spectroscopic parameters were reported. Covalency of rare-earth-oxygen bond was studied in these phosphate glass matrices with the variation of modifier in host glass matrix Using Judd-Ofelt intensity parameters (Omega(2), Omega(4) and Omega(6)), radiative transition probabilities (A) and radiative lifetimes (tau(R)) of certain excited states of Nd3+ and Dy3+ ions are estimated in these glass matrices. From the magnitudes of branching ratios (beta(R)) and integrated absorption cross-sections (Sigma), certain transitions of both the ions are identified for laser excitation. From the emission spectra, peak stimulated emission cross-sections (sigma(P)) are evaluated for the emission transitions observed in all these phosphate glass matrices for both Nd3+ and Dy3+ ions. (C) 2009 Elsevier B.V. All rights reserved.

Electronic structures of electron donor-acceptor complexes: results from ultraviolet photoelectron spectroscopy and molecular orbital calculations

HeI photoelectron spectra of 1:1 electron donor-acceptor complexes are discussed in the light of molecular orbital calculations. The complexes discussed include those formed by BH3, BF3 and SO2. Some systematics have been found in the ionization energy shifts of the complexes compared to the free components and these are related to the strength of the donor-acceptor bond. Hel spectra of hydrogen bonded complexes are discussed in comparison with results from MO calculations. Limitations of such studies as well as scope for further investigations are indicated.

Photodissociation of isomeric dichloroethylenes in the ultraviolet: Effect of the second chlorine atom substitution on the dynamics

We report the Cl-*(P-2(1/2)) production dynamics in the near-UV dissociation of three isomers (cis-, gem-, and trans-) of dichloroethylene using the conventional resonance enhanced multiphoton ionization technique. Substantial amounts of Cl-* are produced in the wavelength range 222-304 nm. The Cl-* quantum yield (phi(*)) i maximum at 304 nm for all the isomers and phi(*)(cis) is markedly higher than phi(*)(gem) and phi(*)(trans) except at 222 nm. Existence of both direct and indirect dissociation pathways at these wavelengths complicates the Cl* production dynamics. The higher value of phi(*)(cis) originates from a large contribution from direct dissociation via the (n, sigma(*)) state.

Steric effects on the ultraviolet absorption of 1,2-enedioic and related systems

1,2-Enedioic systems, being sterically perturbed from planarity do not show the effect of the extended conjugation expected of a (formal) trienic entity. In the absence of a model which approximates to a uniplanar situation, the strategy of replacing an ester group in the enedioates by a cyano (for which less stringent steric demand may be presumed) and noting the correction concomitant to this replacement was adopted to arrive at a notional figure for the position of maximal absorption in the planar enedioates. From this the conclusion, subject to substantiation by molecular mechanical or quantum chemical calculations, was drawn that even the E-isomeric and comparatively less substituted enedioates are highly sterically perturbed. An alternative to an earlier explanation of the bathochromic shift of absorption maxima encountered in the 5-cyclic ene-ester and ene-nitrile, relative to the 6-cyclic analogues (observed also with the enedioates and cyanovinyl ester systems), seen later to have been based on unwarranted premises, has been advanced. A comment on the absorption characteristics of enedioic anhydrides has been appended.