ALBERT

Notes: The electronic energy transfer pathways that occur following collisions between I2 in the E ion-pair electronic state (v=0, J=55) and He and Ar atoms have been determined. The nearby D, D′, and β ion-pair states are populated, but with relative branching ratios that vary with the rare gas collision partner. In He/I2 collisions, the D state is preferentially populated, while Ar/I2 collisions preferentially populate the β electronic state. Bimolecular rate constants and effective hard sphere collision cross sections have been determined for each channel; the cross sections range from 7.0±1.0 Å2 for populating the β state with Ar collisions to 0.9±0.2 Å2 for populating the D′ state with He collisions. For both rare gas collision partners, and all three final electronic states, low vibrational levels are populated, in rough accord with the relevant Franck–Condon factors. There is little propensity observed for population of vibrational levels that are in near resonance with the initially prepared level in the E state. © 2002 American Institute of Physics.

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: 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.

Notes: Spo0A~P is the essential response regulator and transcription factor for sporulation initiation in Bacillus subtilis. The phosphorylation level of Spo0A in the cell is determined by the sensor kinase activity of the phosphorelay, donating phosphoryl groups, and the antagonistic effects of dephosphorylation mediated by the Rap and Spo0E families of phosphatases. In this study, spo0A mutations were generated that encoded proteins less sensitive to the activity of Spo0E than the wild-type protein. The Spo0A substitutions N12K, P60S, L62P and F88L are surface exposed and localize to the same face of the molecule as the active site and in its close proximity on the β1–α1, β3–α3 and β4–α4 loops. The corresponding surface in the Spo0F response regulator was shown previously to be involved in the interaction with the RapB phosphatase, as well as the KinA histidine kinase and the Spo0B phosphotransferase. Thus, residues occupying the same position (N12:Q12, F88:Y84) and the same loops in Spo0A or Spo0F are involved in the interaction with the structurally unrelated Spo0E and RapB phosphatases, respectively, in addition to kinases and phosphotransferase. The specificity in phosphatase target recognition must be the result of side-chain variability within the response regulators and the interactions they promote. The residues involved in Spo0E interaction are identical in all Spo0A orthologues from spore-forming Bacilli encoding Spo0E phosphatases.

Notes: This talk will describe proposed studies of atomic- and nanoscale dynamics in condensed matter which take advantage of the high coherent x-ray flux to be produced by future x-ray free-electron laser (FEL) sources, such as the Linac Coherent Light Source at Stanford. In particular, I will focus on the current status and future prospects for photon correlation spectroscopy using coherent x-rays (XPCS), and the use of the ultrashort pulse structure of the x-ray FEL to observe dynamics into the femtosecond range. © 2002 American Institute of Physics.

Notes: A technique for selective characterization of the structure of free and buried thin-film interfaces by vibrationally resonant sum frequency generation spectroscopy is described. Manipulation of Fresnel coefficients by choice of film thickness on a reflecting substrate allows simultaneous optimization of the signal from the desired interface and minimization of the signal from other interfacial sources. This technique is demonstrated for the free polystyrene (PS)/air and the buried PS/spin-on glass interfaces. Our spectra show that the pendant phenyl group orientation is similar at the buried and free interfaces, with the phenyls pointing away from the bulk PS at each interface.

Notes: We present in situ surface x-ray scattering measurements of PbTiO3 epitaxy by metal–organic chemical-vapor deposition. Oscillations in crystal truncation rod intensity corresponding to layer-by-layer growth are observed under a variety of growth conditions. At lower PbO overpressures, we observe a transition to step-flow growth and an increased rate of recovery after growth, indicating a higher surface mobility. © 2002 American Institute of Physics.

Notes: Classical Mendelian experiments were conducted to determine the genetics and inheritance of quinclorac and acetolactate synthase (ALS)-inhibitor resistance in a biotype of Galium spurium. Plants were screened with the formulated product of either quinclorac or the ALS-inhibitor, thifensulfuron, at the field dose of 125 or 6 g active ingredient (a.i.) ha−1 respectively. Segregation in the F2 generation indicated that quinclorac resistance was a single, recessive nuclear trait, based on a 1 : 3 segregation ratio [resistant : susceptible (R : S)]. Resistance to ALS inhibitors was due to a single, dominant nuclear trait, segregating in the F2 generation in a 3 : 1 ratio (R : S). The genetic models were confirmed by herbicide screens of F1 and backcrosses between the F1 and the S parent. F2 plants that survived quinclorac treatment set seed and the resulting F3 progeny were screened with either herbicide. Quinclorac-treated F3 plants segregated in a 1 : 0 ratio (R : S), hence F2 progenitors were homozygous for quinclorac resistance. In contrast, F3 progeny segregated into three ratios: 1 : 0, 3 : 1 and 0 : 1 (R : S) in response to ALS-inhibitor treatment. This segregation pattern indicates that their F2 parents were either homozygous or heterozygous for ALS-inhibitor resistance. Therefore, there were clearly two distinct resistance mechanisms encoded by two genes that were not tightly linked as demonstrated by segregation patterns of the F3.