ALBERT

Notes: The vibrational relaxation dynamics of CO chemisorbed on small Pt and Rh particles supported on SiO2 has been investigated by picosecond time-resolved infrared transient bleaching experiments. A vibrational T1 lifetime of ≈7 ps has been observed for several different samples, independent of polarization, pump intensity, and sample temperature from 100–400 K. A 1:3 isotopic dilution has no effect upon T1. This T1 lifetime is a factor of 10–50 times shorter than T1 reported for metal carbonyl cluster compounds in solution and on SiO2 supports. Two possible mechanisms are considered to account for the rapid T1 decay; redistribution of the energy throughout the broad CO vibrational band, and relaxation directly to electron–hole pairs in the metal particles.

Notes: The A 3Π1←X 1Σ+ laser-induced fluorescence excitation spectrum of the NeIBr van der Waals complex is reported and analyzed to extract information regarding the structure and vibrational predissociation dynamics of the complex. While no definitive geometric information regarding NeIBr is obtained, our data indicate that a linear geometry is at least plausible. The vibrational predissociation lifetimes are a strong function of A state vibrational level and range from 2.6 to 23 ps. The variation in lifetime with vibrational level is consistent with the results of previous measurements on rare gas–halogen complexes, particularly NeBr2.

Notes: Vibrational overtone photodissociation is used to examine the spectroscopy and vibrational predissociation lifetimes of HN3 in its ground electronic state. Direct overtone pumping of the N–H stretching levels 5νNH and 6νNH prepares molecules in selected states (v,J,K) near 15 100 and 17 700 cm−1 of vibrational energy; spin-forbidden NH(X 3 Σ−) dissociation fragments are detected by laser-induced fluorescence. Photodissociation spectra of beam-cooled HN3 display mixing of individual rotational levels of the nνNH vibrations with several background states, with derived coupling matrix elements in the range 0.01–0.1 cm−1. Vibrational predissociation lifetimes of mixed components of 5νNH are state specific, with variations of a factor of 2 for only 0.1 cm−1 energy differences. Average lifetimes for low J, K are 210 ns for 5νNH and 0.95 ns for 6νNH. The ratio of decay rates for the two overtone levels, k(6νNH)/k(5νNH)=220, is much greater than predicted by statistical theory, which gives a ratio of 4.

Notes: The effect of growth conditions on the stability of α-Sn films grown by molecular beam epitaxy on CdTe is studied. The growth conditions considered are substrate orientation, thickness, growth rate, and substrate temperature. The transition temperature from α-Sn to β-Sn, as determined by optical microscopy, is used as the measure of stability. It is shown that CdTe(110) is a somewhat better orientation than CdTe(100), and CdTe(111)B is totally unacceptable for the growth by molecular beam epitaxy of α-Sn films. The transition temperature from α-Sn to β-Sn shows a dependence on the total film thickness, with thinner films having a somewhat higher transition temperature than thicker. The quality of the films is the best when the growth rate is about 0.5 A(ring)/s and the growth temperature is about 75 °C. Since the transition from α-Sn to β-Sn starts at defects in the film, improving the quality of the film by lowering the growth rate and raising the growth temperature raises the transition temperature.

Notes: Time-resolved x-ray scattering studies of phase transition kinetics have been carried out using the wide-bandpass monochromator and fast linear position-sensitive detector system at the IBM/MIT beamline X-20C at the National Synchrotron Light Source (NSLS). We report here on the instrumentation that has been developed for these studies, and in particular on the methods used to measure, change, and control sample temperature with millisecond resolution.

Notes: The mechanism of the reaction CH4+O(1D2)→CH3+OH was investigated by ultrafast, time-resolved and state-resolved experiments. In the ultrafast experiments, short ultraviolet pulses photolyzed ozone in the CH4⋅O3 van der Waals complex to produce O(1D2). The ensuing reaction with CH4 was monitored by measuring the appearance rate of OH(v=0,1;J,Ω,Λ) by laser-induced fluorescence, through the OH A←X transition, using short probe pulses. These spectrally broad pulses, centered between 307 and 316 nm, probe many different OH rovibrational states simultaneously. At each probe wavelength, both a fast and a slow rise time were evident in the fluorescence signal, and the ratio of the fast-to-slow signal varied with probe wavelength. The distribution of OH(v,J,Ω,Λ) states, Pobs(v,J,Ω,Λ), was determined by laser-induced fluorescence using a high-resolution, tunable dye laser. The Pobs(v,J,Ω,Λ) data and the time-resolved data were analyzed under the assumption that different formation times represent different reaction mechanisms and that each mechanism produces a characteristic rovibrational distribution. The state-resolved and the time-resolved data can be fit independently using a two-mechanism model: Pobs(v,J,Ω,Λ) can be decomposed into two components, and the appearance of OH can be fit by two exponential rise times. However, these independent analyses are not mutually consistent. The time-resolved and state-resolved data can be consistently fit using a three-mechanism model. The OH appearance signals, at all probe wavelengths, were fit with times τfast(approximate)0.2 ps, τinter(approximate)0.5 ps and τslow(approximate)5.4 ps. The slowest of these three is the rate for dissociation of a vibrationally excited methanol intermediate (CH3OH*) predicted by statistical theory after complete intramolecular energy redistribution following insertion of O(1D2) into CH4. The Pobs(v,J,Ω,Λ) was decomposed into three components, each with a linear surprisal, under the assumption that the mechanism producing OH at a statistical rate would be characterized by a statistical prior. Dissociation of a CH4O* intermediate before complete energy randomization was identified as producing OH at the intermediate rate and was associated with a population distribution with more rovibrational energy than the slow mechanism. The third mechanism produces OH promptly with a cold rovibrational distribution, indicative of a collinear abstraction mechanism. After these identifications were made, it was possible to predict the fraction of signal associated with each mechanism at different probe wavelengths in the ultrafast experiment, and the predictions proved consistent with measured appearance signals. This model also reconciles data from a variety of previous experiments. While this model is the simplest that is consistent with the data, it is not definitive for several reasons. First, the appearance signals measured in these experiments probe simultaneously many OH(v,J,Ω,Λ) states, which would tend to obfuscate differences in the appearance rate of specific rovibrational states. Second, only about half of the OH(v,J,Ω,Λ) states populated by this reaction could be probed by laser-induced fluorescence through the OH A←X band with our apparatus. Third, the cluster environment might influence the dynamics compared to the free bimolecular reaction.

Notes: The collision-induced electronic energy transfer that occurs when I2 in the E(0g+) ion-pair electronic state collides with ground electronic state I2 has been investigated. We prepare I2 in single rotational levels in v=0 of the E state using two-color double resonance laser excitation. The resulting emission spectrum shows that the nearby (ΔTe=−385 cm−1) D(0u+) electronic state is populated. The cross section for collision-induced E→D energy transfer is found to be 18±3 Å2. A range of D state vibrational levels are populated, consistent with a model in which overlap between the initial and final vibrational wave functions is important, but modulated by propensities for small vibrational energy gaps and those energy gaps that are closely matched to the v=0→v=1 energy separation in the I2(X) collision partner. © 2001 American Institute of Physics.

Notes: Summary Low yield in seed crops of perennial ryegrass is related to low fertilization efficiency and low temperature during anthesis. To study the effect of genotype and temperature on pollen performance, we conducted greenhouse experiments at controlled temperatures. Individual florets of four genotypes that are known to differ in seed production were hand pollinated at four temperatures (14°, 18°, 22°, 26° C) both in vivo and via a semiin-vitro method involving excised florets on agar. Pollen germination and tube growth were determined with UV-fluorescence microscopy and scored in six classes at 2 h after pollination in vitro and after 0.5, 2 and 5 h in vivo. In vitro, both genotype and temperature had a significant effect on the performance of self-pollen. Pollen tube growth increased with temperature. In cross-pollinations, the pistil parent had a significant effect on pollen tube growth, and there was also a significant pistil-by-temperature interaction. In vivo, genotype and temperature significantly affected pollen performance. The genotype-by-temperature interaction was only significant 5 h after pollination. One genotype with low seed yield was pseudoself-compatible and was a relatively poor mother after cross-pollination. The effects of genotype and temperature on the growth of self-pollen might be exploited in a breeding programme.

Notes: Abstract Two recent studies using tree aggregations to analyze forest age-structure stability and past forest structure are flawed. A better understanding of aggregation dynamics is needed before aggregation analysis is used in forest management.

Notes: Abstract Perovskite (CaTiO3) has been exposed to hydrothermal chemical attack in aqueous solution. Dependences on temperature (150 to 250°C) and on duration of attack (1 to 35 days) have been investigated. It was found that a precipitate surface layer was formed. The thickness of this layer ranged from a few monolayers to several hundred nanometres for the least and the most severe hydrothermal conditions, respectively. The composition of the layer, as deduced by surface analytical techniques, suggests that (i) there is congruent dissolution of the perov skite surface, (ii) a TiO2 precipitate layer is formed, and (iii) the presence of silica and CO2 in solution do not appear to affect substantially the mechanism or the rate of dissolution.