On the photochemistry of IONO2: absorption cross section (240-370 nm) and photolysis product yields at 248 nm.

The absolute absorption cross section of IONO(2) was measured by the pulsed photolysis at 193 nm of a NO(2)/CF(3)I mixture, followed by time-resolved Fourier transform spectroscopy in the near-UV. The resulting cross section at a temperature of 296 K over the wavelength range from 240 to 370 nm is given by log(10)(sigma(IONO(2))/cm(2) molecule(-1)) = 170.4 - 3.773 lambda + 2.965 x 10(-2)lambda(2)- 1.139 x 10(-4)lambda(3) + 2.144 x 10(-7)lambda(4)- 1.587 x 10(-10)lambda(5), where lambda is in nm; the cross section, with 2sigma uncertainty, ranges from (6.5 +/- 1.9) x 10(-18) cm(2) at 240 nm to (5 +/- 3) x 10(-19) cm(2) at 350 nm, and is significantly lower than a previous measurement [J. C. Mössinger, D. M. Rowley and R. A. Cox, Atmos. Chem. Phys., 2002, 2, 227]. The photolysis quantum yields for IO and NO(3) production at 248 nm were measured using laser induced fluorescence of IO at 445 nm, and cavity ring-down spectroscopy of NO(3) at 662 nm, yielding phi(IO)

An experimental and theoretical study of the reactions OIO+NO and OIO+OH.

The kinetics of the reaction OIO+NO were studied by pulsed laser photolysis/time-resolved cavity ring-down spectroscopy, yielding k(235-320 K)=7.6(+4.0)(-3.1) x 10(-13) exp[(607+/-128)/T] cm3 molecule-1 s-1. Quantum calculations on the OIO+NO potential-energy surface show that the reactants form a weakly bound OIONO intermediate, which then dissociates to the products IO+NO2. Rice-Ramsberger-Kassel-Markus (RRKM) calculations on this surface are in good accord with the experimental result. The most stable potential product, IONO2, cannot form because of the significant rearrangement of OIONO that would be required. The reaction OIO+OH was then investigated by quantum calculations of the relevant stationary points on its potential-energy surface. The very stable HOIO2 molecule can form by direct recombination, but the bimolecular reaction channels to HO2+IO and HOI+O2 are closed because of significant energy barriers. RRKM calculations of the HOIO2 recombination rate coefficient yield krec,0=1.5x10(-27) (T/300 K)(-3.93) cm6 molecule-2 s-1, krec,infinity=5.5x10(-10) exp(46/T) cm3 molecule-1 s-1, and Fc=0.30. The rate coefficients of both reactions are fast enough around 290 K and 1 atm pressure for these reactions to play a potentially important role in the gas phase and aerosol chemistry in the marine boundary layer of the atmosphere.

Light-emitting diode (LED) polymerisation of dental composites: flexural properties and polymerisation potential.

The clinical performance of light polymerised dental composites is greatly influenced by the quality of the light-curing unit (LCU) used. Commonly used halogen LCUs have some specific drawbacks such as decreasing of the light output with time. This may result in low degree of monomer conversion of the composites with negative clinical implications. Previous studies have shown that blue-light-emitting diode (LED) LCUs have the potential to polymerise dental composites without having the drawbacks of halogen LCUs. Despite the relatively low irradiance of current LED LCUs, their efficiency is close to that of conventional halogen LCUs with more than twice the irradiance. This phenomenon has not been explained fully yet. Hence, more tests of the LED LCU's effectiveness and of the mechanical properties of oral biomaterials processed with LED LCUs need to be carried out. This study investigates the flexural properties of three different composites with three different shades, which were polymerised with either a commercial halogen LCU or an LED LCU, respectively. In most cases no significant differences in flexural strength and modulus between composites polymerised with a halogen LCU or an LED LCU, respectively, were found. A simple model for the curing effectiveness based on the convolution absorption spectrum of the camphorquinone photoinitiator present in composites and the emission spectra of the LCUs is presented.

Depth of cure and compressive strength of dental composites cured with blue light emitting diodes (LEDs).

OBJECTIVE: The primary objective of this pilot study was to test the hypotheses that (i) depth of cure and (ii) compressive strength of dental composites cured with either a light emitting diode (LED) based light curing unit (LCU) or a conventional halogen LCU do not differ significantly. The second objective of this study was to characterise irradiance and the emitted light spectra for both LCUs to allow comparisons between the units. METHODS: Dental composite (Spectrum TPH, shades A2 and A4) was cured for 40 s with either a commercial halogen LCU or a LED LCU, respectively. The LED LCU uses 27 blue LEDs as the light source. The composites' depth of cure was measured for 10 samples of 4 mm diameter and 8 mm depth for each shade with a penetrometer. The results were compared using a Student's t-test. Compressive strengths were determined after 6 and 72 h, for six samples of 4 mm diameter and 6 mm depth for each shade after being polymerised for 40 s from each end of the mould. Groups were compared using a three way ANOVA. RESULTS: The conventional halogen LCU cured composites significantly (p < 0.05) deeper (6.40 mm A2, 5.19 mm A4) than did the LED LCU (5.33 mm A2, 4.27 mm A4). Both units cured the composite deeper than required by both ISO 4049 and the manufacturer. A three way ANOVA showed that there were no significant differences in the compressive strengths of samples produced with either the LED LCU or the halogen LCU (p = 0.460). Significant differences in compressive strength of samples stored for 6 and 72 h (p = 0.0006) and of samples of different shades (p = 0.035) were found as confirmed by the three way ANOVA. The light spectra of both units differed strongly. While the halogen LCU showed a broad distribution of wavelengths with a power peak at 497 nm, the LED LCU emitted most of the generated light at 465 nm. The LED LCU produced a total irradiance of 350 mW cm-2 whereas the halogen LCU produced a total irradiance of 755 mW cm-2. SIGNIFICANCE: The results showed that both units provided sufficient output to exceed minimum requirements in terms of composites' depth of cure according to ISO 4049 and the depth of cure and the composites' compressive strength stated by the manufacturer. Compressive strengths of dental composites cured under laboratory conditions with a LED LCU were statistically equivalent to those cured with a conventional halogen LCU. With its inherent advantages, such as a constant power output over the lifetime of the diodes, LED LCUs have great potential to achieve a clinically consistent quality of composite cure.

Dental composite depth of cure with halogen and blue light emitting diode technology.

OBJECTIVES: To test the hypothesis that a blue light emitting diode (LED) light curing unit (LCU) can produce an equal dental composite depth of cure to a halogen LCU adjusted to give an irradiance of 300 mWcm-2 and to characterise the LCU's light outputs. MATERIALS AND METHODS: Depth of cure for three popular composites was determined using a penetrometer. The Student's t test was used to analyse the depth of cure results. A power meter and a spectrometer measured the light output. RESULTS: The spectral distribution of the LCUs differed strongly. The irradiance for the LED and halogen LCUs were 290 mWcm-2 and 455 mWcm-2, when calculated from the scientific power meter measurements. The LED LCU cured all three dental composites to a significantly greater (P < 0.05) depth than the halogen LCU. CONCLUSIONS: An LED LCU with an irradiance 64% of a halogen LCU achieved a significantly greater depth of cure. The LCU's spectral distribution of emitted light should be considered in addition to irradiance as a performance indicator. LED LCUs may have a potential for use in dental practice because their performance does not significantly reduce with time as do conventional halogen LCUs.

Second-order nonlinearities of polycrystalline molecular films studied on a 20-fs time scale.

Second-harmonic generation in polycrystalline pentacene films of submicrometer thickness by pulses of 18-fs duration is studied. We observe a second-order nonlinearity of as much as d(eff) = 0.045 pm/V, which is resonantly enhanced at wavelengths near 790 nm. Off-resonance autocorrelation studies demonstrate a quasiinstantaneous nonlinear response of the material, whereas experiments on resonance point to a finite response time T(2) of the order of 15 fs.

Generation of 16-fs pulses at 425 nm by extracavity frequency doubling of a mode-locked Ti:sapphire laser.

An efficient doubling scheme capable of producing 16-fs pulses centered at 425 nm with an average power of 40 mW is described. The system uses 15-fs pulses from a continuous-wave mode-locked Ti:sapphire oscillator centered at 850 nm. The pulse characteristics resulting from doubling with beta-barium borate crystals of various lengths are presented. The results compare favorably with previous attempts at intracavity doubling and provide a more convenient route to femtosecond experiments with fully synchronized second-harmonic radiation.