ALBERT

Notes: The vibrational dynamics of excited CO layers on Pt(111) were studied using infrared (IR) pump–probe methods. Resonant IR pulses of 0.7 ps duration strongly pumped the absorption line (ν≈2106 cm−1 ) of top-site CO. Weak probe pulses delayed a time tD after the pump were reflected from the CO-covered Pt(111) surface, and dispersed in a monochromator to determine the absorption spectrum of the vibrationally excited CO band, with time resolution 〈1 ps and monochromator resolution 〈1 cm−1. Transient spectra were obtained as a function of CO coverage, surface temperature, and laser fluence. Complex spectra for tD〈0 show features characteristic of a perturbed free induction decay, which are expected based on multiple-level density-matrix models. For tD≥0, the CO/Pt absorption exhibits a shift to lower frequency and an asymmetric broadening which are strongly dependent on fluence (1.3–15 mJ/cm2 ). Spectra return to equilibrium (unexcited) values within a few picoseconds. These transient spectral shifts and the time scale for relaxation do not depend (within experimental error) on coverage for 0.1≤aitch-thetaCO≤0.5 ML or on temperature for 150≤Ts≤300 K. A model for coupled anharmonic oscillators qualitatively explains the tD〉0 spectra in terms of a population-dependent decrease in frequency of the one-phonon band, as opposed to a transition involving a true CO(v=2) two-phonon bound state. The rapid relaxation time and its insensitivity to Ts and aitch-thetaCO are consistent with electron–hole pair generation as the dominant decay mechanism.

Notes: NH stretching overtone and combination states in HN3 X˜ 1A' were excited by IR–visible double resonance pumping and by direct overtone pumping in the range 6ν1 (17 670 cm−1) to 7ν1 (20 070 cm−1). NH fragments in the a 1Δ and X 3Σ− states were detected by laser induced fluorescence with sub-Doppler resolution to determine branching ratios, correlated fragment rotational state and kinetic energy distributions, and fragment vector correlations. The spin-forbidden triplet channel was accessible to all states excited, while the threshold for the singlet channel was determined to lie in the range 18 190 to 18 755 cm−1. The measured energy release places limits on the HN–NN bond energy, and the heights of barriers to reaction. The barrier in the singlet exit channel is at least 540 cm−1. The singlet channel accessed by 7ν1 dissociation is characterized by a Boltzmann-like NH rotational distribution (〈J NH〉≈3.5), highly excited N2 rotations (〈JN2〉 ≥ 20), and total translational energy release peaked away from zero (〈ET〉≈1350 cm−1). Vector correlations and Λ-doublet propensities indicate that nonplanar dissociation processes influence the NH rotations, but become less important for higher NH rotational states. The principal correlations are a strong positive recoil anisotropy (β≈0.6), a weak positive v–J correlation (βvJ≈0.17), and a JNH-dependent Λ-doublet propensity. A model using parent vibrational motion projected onto fragment rotation is suggested to explain these observations. The triplet channel exhibits similar NH and N2 rotational state distributions, with most of the available energy (substantially greater than in the singlet channel) appearing as fragment kinetic energy.

Notes: Nonadiabatic interactions in the NeICl van der Waals complex have been explored in the lowest energy triad of ICl ion-pair states (∼39 000 cm−1). Dispersed fluorescence measurements reveal emission characteristic of multiple ion-pair electronic states, with the relative contributions from the E(0+), β(1), and D'(2) states changing with the initial ICl vibrational excitation (vICl). Emission directly from NeICl (vICl=0) complexes indicates that the initially prepared NeICl levels have mixed electronic character and that the ICl electronic parentage changes with the initial van der Waals vibrational level selected. NeICl complexes prepared with 1–4 quanta of ICl stretch undergo rapid vibrational predissociation with a strong propensity for ΔvICl=−1 relaxation. The electronic state(s) populated in the ICl fragments differ from the mixed electronic character of the initially prepared level, demonstrating that vibrational predissociation is accompanied by nonadiabatic electronic state changing processes. The observed final state selectivity may be attributed to the relative strength of the nonadiabatic couplings between the initial NeICl bound state and the final ICl states or a momentum gap rationale based on the overlap between the NeICl bound state wave function and the highly oscillatory continuum wave function of the separating fragments.

Notes: The transient infrared response of CO/Pt(111) following picosecond visible excitation is reported. A spectrally broad decrease in reflectivity correlates with heating of the Pt lattice, and an observed shift in the CO(v=0→1) transition is interpreted as heating of the 60 cm−1 in-plane frustrated translational mode. A phenomenological three temperature model that assumes the adsorbate vibrational temperature Tads exclusively couples to either the electronic temperature Te (with a time constant τe) or to the lattice temperature Tlat (with a time constant τlat) describes the temporal response of the adsorbate vibrations. The lattice phonon temperature Tlat(z,t) and measured temperature dependence of the optical constants predict the observed spectrally broad reflectivity change. Density matrix methods model the infrared response of the transiently heated molecule. Limits of τe=2±1 ps or τlat〈1 ps are established by comparison of predicted spectra and the data.

Notes: An experimental study was carried out to investigate turbulent mixing and entrainment across a density interface subjected to velocity shear. The flow configuration consisted of a salinity (stably) stratified two-fluid system with a driven upper turbulent layer and a quiescent lower layer. The experiments were performed in an Odell–Kovasznay tank and the mean flow in the upper layer was generated by using a conventional disk pump. The velocity and salinity measurements were made using a laser-Doppler anemometer and conductivity probes, respectively, and (quantitative) flow visualization was performed using the laser-induced fluorescence LIF technique. The refractive indices of upper and lower layers were matched, using salt and alcohol, to facilitate the use of laser-based flow diagnostic techniques. The measurements show that the rms velocity fluctuation u in bulk of the mixed layer scales well with the mean velocity jump Δu across the interface. The Thorpe, buoyancy, overturning, and integral length scales, as well as the maximum Thorpe displacement in the mixed layer, were also found to be proportional to the depth h of the upper mixed layer.The structure of the entrainment interface was found to depend strongly on the bulk Richardson number Ri (=Δb h/u2), where Δb is the buoyancy jump across the interfacial layer. At lower Ri, the entrainment occurred rapidly, as in a nonstratified fluid, but as Ri increases, the entrainment rate becomes a strong function of Ri: under the latter conditions, the interfacial wave breaking and Kelvin–Helmholtz instabilities were common features. At still higher Ri, the entrainment rate becomes vanishingly small and the interfacial mixing events were found to be controlled by the molecular diffusive effects. The measurement of the interfacial-layer thickness using LIF shows that it is much thinner than that measured using less-accurate techniques such as traversing probes. The nondimensional rms amplitude of the interfacial distortions at moderate and high Ri was found to be a strong function of Ri. The interfacial instabilities cause the formation of isolated mixing patches within the interface, which, when collapsed, form horizontal intrusions. The experimental measurements were in agreement with theoretical formulations based on scaling arguments.

Notes: The effect of five herbicide safeners on preventing maize (Zea mays L.) injury by acetochlor [N-(2-ethyl-6-methyl-phenyl)-N-(ethoxymethyl)-chloroacetamide], their influence on herbicide uptake and metabolism to a glutathione (GSH) conjugate as well as on GSH content and glutathione S-transferase activity (GST) in untreated and herbicide with/without safener-pre-treated 4-day-old seedlings were determined. The safeners studied were: AD-67 (N-di-chloroacetyl-1-oxa-4-azaspiro-4-5-decane), BAS-145138 [1-dichloroacetyl-hexahydro-3,3,8a-trimethyl-pyrrolo(l,2-a)pyrimidin-6(2H)-one], dichlormid (N, A,-diallyl-2,2-dichlo-roacetamide), DKA-24 (N, N2-diallyl-N2dichloroacetylglycineamide) and MG-191 (2-dichloromethyl-2-methyl-1,3-dioxolane). All safeners significantly increased [14C]acetochlor uptake and metabolism rate, maize GSH content and GST activity. Seedlings receiving BAS-145138 pre-treatment metabolized almost 70% of the absorbed [14C]acetochlor within 10 min.Safener-enhanced GST activity was always found to be higher when [14C]acetochlor was used as the substrate compared with CDNB (1-chloro-2,4-dinitrobenzene). Although DKA-24 had a significantly lower influence on both herbicide metabolism and GST activity, it was nearly as effective a safener as BAS-145138, while the others provided no or poor protection to maize from acetochlor injury when they were not incorporated in the soil. Effets d'antidotes sur la toxicité, la pénétration et le métabolisme de I'acétochlore chez le mats etsur l'activité glutathion S-transférase Cinq antidotes d'herbicides diminuaient la toxicité de 1'acétochlore [N-(2-éthyl-6-méthyl-phényl)-N-(éthoxyméthyl)-chloroacétamide] à I'égard du maïs (Zea mays L.). Lew effet sur l'absorption de l'herbicide et sur son métabolisme en un conjugué avec le glutathion (GSH), de même que leur effet sur la teneur en GSH et 1'activité glutathion 5-transférase (GST) ont étéétudiés sur des maïs âgés de 4 jours. Les antidotes étaient: l'AD-67 (N-dichloroacétyl-1-oxa-4-azaspiro-4,5-décane), le BAS-145138 [1 -dichloroacétyl-hexahydro-3,3,8a-triméthyl-pyrrolo(l,2-a) pyrimidine-6(2H)-one], le di-chlormide (N, N-diallyl-2,2-dichloracétamide), le DKA-24 (N, N2-diallyl-N2-dichloracétylgly-cineamide] et le MG-191 (2-dichlorométhyl-2-méthyl-l,3-dioxolane). Tous les antidotes augmentaient de manière significative 1'absorption et le métabolisme de I'acétochlore 14C, ainsi que la teneur du maïs en GSH et son activité GST. Les jeunes plantes prétraitées avec le BAS-145138 métabolisaient en 10 min près de 70% de I'acétochlore 14C absorbé. L'activité GST stimulée par 1'antidote était toujours plus élevée avec I'acétochlore 14C comme substrat qu'avec le CDNB (1-chloro-2,4-dinitrobenzène).Le DKA-24 avait un effet significativement plus faible que le BAS-145138 sur le métabolisme de l'herbicide et sur l'activité GSH, mais son action antidote était presque aussi importante. Les autres produits n'apportaient au maïs qu'une protection faible ou nulle contre l'acétochlore quand ils n'étaient pas incorporés au sol. Wirkung von Safenern auf die Phytotoxizität, Aufnahme und Metabolismus von Acetochlor und die Glutathion-S-Transferase-Aktivität in Mais Die Wirkung von 5 Safenern (AD-67, BAS-145138, Dichlormid, DKA-24 und MG-191; chemische Bezeichnungen s.o.) auf die Phytotoxizität von Acetochlor für Mais (Zea mays L.) und ihr Einfluß auf die Aufnahme des Herbizids und Metabolismus zu einem Glutathion-(GSH-) Konjugat und auf die Glutathion-S-Transferase-(GST-)Aktivität wurde an 4 Tage alten Keimpflanzen untersucht. Durch die Vorbehandlung mit den Safenern wurden die [14C]-Acetochlor-Aufnahme- und -Metabolierungsrate, der GSH-Gehalt und die GST-Ak-tivität signifikant erhöht. Mit BAS-145138 vorbehandelte Keimpflanzen metabolisierten fast 70% des absorbierten [14C]-Acetochlor innerhalb von 10 min. Die durch die Safener erhöhte GST-Aktivität bei [14C]-Acetochlor als Substrat war im Vergleich zu Chlordinitroben-zen immer höher. Obwohl DKA-24 einen signifikant geringeren Einfluß sowohl auf den Herbizidmetabolismus als auch auf die GST-Aktivität hatte, war es fast so wirkungsvoll wie BAS-145138, während die anderen ohne Einarbeitung in den Boden für den Mais keinen oder geringen Schutz gegen Schäden durch Acetochlor boten.