ALBERT

Notizen: 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.

Notizen: 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.

Notizen: The spatial structure of several exploited species within and among known populations of the Northwest Atlantic is reviewed using past and current knowledge. For each species, the coherence of existing management units with the spatial scale of population dynamics (populations, sub-populations, and spawning components) is summarized. The implications of this match or mismatch of spatial scales in the maintenance of biodiversity within and among populations are also discussed.

Notizen: The ratios of stable isotopes 18O/16O and 13C/12C, in sagittal otolith carbonate from two tropical demersal teleosts, red emperor Lutjanus sebae and Rankin cod Epinephelis multinotatus, from several locations in northern Western Australia, differed between sites. On a broad scale, fish from the four locations, Shark Bay, Ningaloo, Pilbara, and Broome had stable isotope values that were sufficiently different to indicate separate stocks, and it is appropriate to manage these populations of the two species independently in these areas. On a smaller scale, there may be limited mixing of these species between the Pilbara trawl fishery and the trap and line fisheries operating out of Onslow and Broome. Values of stable oxygen isotopes were strongly related to sea surface temperature, although there were some sites in shallow water where low values of stable oxygen isotopes indicated that fish were living in warm water. The use of stable oxygen and carbon isotope values is a valuable, cost effective method of determining the degree of mixing of fish stocks.

Notizen: Analysis of nine tetranucleotide microsatellite loci for Atlantic herring at five locations in the Northwest Atlantic including the Bras d'Or Lakes shows considerable genetic variation and significant population structure within the Coastal Nova Scotia management component, and among coastal populations and herring collected from Georges Bank. However, results are also consistent with gene flow across the Gulf of Maine. The magnitude of differentiation between the Bras d'Or Lakes sample and all others considered was sufficient to warrant further investigation. These data support the precautionary spawning-ground based management approach implemented in this area.