Oxidation and the effects of high temperature exposures on notched fatigue life were considered for a powder metallurgy processed supersolvus heat-treated ME3 disk superalloy. The isothermal static oxidation response at 704 °C, 760 °C, and 815 °C was consistent with other chromia forming nickel-based superalloys: a TiO 2 -Cr 2 O 3 external oxide formed with a branched Al 2 O 3 internal subscale that extended into a recrystallized γ'-dissolution layer. These surface changes can potentially impact disk durability, making layer growth rates important. Growth of the external scales and γ'dissolution layers followed a cubic rate law, while Al 2 O 3 subscales followed a parabolic rate law. Cr-rich M 23 C 6 carbides at the grain boundaries dissolved to help sustain Cr 2 O 3 growth to depths about 12 times thicker than the scale.The effect of prior exposures was examined through notched low cycle fatigue tests performed to failure in air at 704 °C. Prior exposures led to pronounced debits of up to 99 % in fatigue life, where fatigue life decreased inversely with exposure time. Exposures that produced roughly equivalent 1 µm thick external scales at the various isotherms showed statistically equivalent fatigue lives, establishing that surface damage drives fatigue debit, not exposure temperature. Fractographic evaluation indicated the failure mode for the pre-exposed specimens involved surface crack initiations that shifted with exposure from predominately single intergranular initiations with transgranular propagation to multi-initiations from the cracked external oxide with intergranular propagation. Weakened grain boundaries at the surface resulting from the M 23 C 6 carbide dissolution are partially responsible for the intergranular cracking. Removing the scale and subscale while leaving a layer where M 23 C 6 carbides were dissolved did not lead to a significant fatigue life improvement, however, also removing the M 23 C 6 carbide dissolution layer led to nearly full recovery of life, with a transgranular initiation typical to that observed in unexposed specimens.
We have studied, experimentally and theoretically, the ionization probability of carbonyl sulfide (OCS) molecules in intense linearly-polarized 800 nm laser pulses as a function of the angle between the molecular axis and the laser polarization. Experimentally, the molecules are exposed to two laser pulses with a relative time delay. The first, weaker pulse induces a nuclear rotational wave packet within each molecule such that the ensemble exhibits preferential alignment in the laboratory frame at specific times. The second, stronger pulse induces ionization, and the variation in single and double ionization yields is measured as a function of the delay between the two pulses. The angular-dependence of the ionization yield is extracted by fitting the delay-dependent yields to a sum of delay-dependent moments of the rotational wave packet's angular distribution. We compute these same angular-dependent strong-field ionization yields for OCS using time-dependent density functional theory (TDDFT). For the single ionization case, our measurements agree well with TDDFT calculations and with previous experiments. Furthermore, analysis of the simulated one-body density reveals that, when averaged over a laser cycle, the resulting hole is delocalized across the molecule for light polarized perpendicular to the molecular axis, and mostly localized on the sulfur for parallel polarization. This suggests that preferential molecular alignment is a key parameter for controlling charge migration dynamics initiated by strong-field ionization. For double ionization, the agreement between experiment and theory is less compelling, reflecting the substantial challenges of computing double ionization yields using TDDFT methods.
We study, experimentally and theoretically, the ionization probability of singly halogenated methane molecules, CH3Cl and CH3Br, in intense linearly polarized 800 nm laser pulses as a function of the angle between the molecular axis and the laser polarization. Experimentally, the molecules are exposed to two laser pulses with a relative time delay. The first, weaker pulse induces a nuclear rotational wave packet within the molecules, which are then ionized by the second, stronger pulse. The angle-dependent ionization yields are extracted from fits of the measured delay-dependent ionization signal to a superposition of moments of the rotational wave packet’s angular distribution. Angle-dependent strong-field ionization (SFI) yields are also calculated using time-dependent density functional theory. Good agreement between measurements and theory is obtained. Interestingly, we find a marked difference between the angle-dependence of the ionization yields for these two halomethane species despite the similar structure of their highest occupied molecular orbitals. Calculations reveal that these differences are a result of multichannel (CH3Cl) vs single-channel (CH3Br) ionization and of increased hole localization on Br vs Cl. By adding calculations for CH3F, we can discern clear trends in the ionization dynamics with increasing halogen mass. These results are illustrative, as chemical functionalization and molecular alignment are likely to be important parameters for initiating and controlling charge migration dynamics via SFI.
We present molecular-frame measurements of the recombination dipole matrix element (RDME) in CO2, N2O, and carbonyl sulfide (OCS) molecules using high-harmonic spectroscopy. Both the amplitudes and phases of the RDMEs exhibit clear imprints of a two-center interference minimum, which moves in energy with the molecular alignment angle relative to the laser polarization. We find that whereas the angle dependence of this minimum is consistent with the molecular geometry in CO2 and N2O, it behaves very differently in OCS; in particular, the phase shift which accompanies the two-center minimum changes sign for different alignment angles. Our results suggest that two interfering structural features contribute to the OCS RDME, namely, (i) the geometrical two-center minimum and (ii) a Cooper-like, electronic-structure minimum associated with the sulfur end of the molecule. We compare our results to ab initio calculations using time-dependent density functional theory and present an empirical model that captures both the two-center and the Cooper-like interferences. We also show that the yield from unaligned samples of two-center molecules is, in general, reduced at high photon energies compared to aligned samples, due to the destructive interference between molecules with different alignments.
We have determined spectral phases of Ne autoionizing states from XUV-MIR attosecond interferometric measurements and ab initio full-electron time-dependent theoretical calculations in an energy interval where several of these states are coherently populated. The retrieved phases exhibit a complex behavior as a function of photon energy, which is the consequence of the interference between paths involving various resonances. In spite of this complexity, we show that phases for individual resonances can still be obtained from experiment by using an extension of the Fano model of atomic resonances. As simultaneous excitation of several resonances is a common scenario in many-electron systems, the present work paves the way to reconstruct electron wave packets coherently generated by attosecond pulses in systems larger than helium.
International audienceHigh-order-harmonic generation (HHG) is a tabletop and tunable source of extreme ultraviolet (XUV) light. Its flexibility was lately evidenced by the production of Laguerre-Gaussian (LG) modes in the XUV with a known azimuthal index. Here we investigate the role of the radial index of LG modes in HHG. We show both numerically and experimentally that the mode content of the emitted XUV radiation can be tuned by controlling the weight of the different quantum trajectories involved in the process. The appearance of high-order radial modes is finally linked to the atomic dipole phase of HHG. These results extend the capabilities of shaping the spatial mode of ultrashort XUV pulses of light
We demonstrate high-harmonic spectroscopy in many-electron molecules using time-dependent density-functional theory. We show that a weak attosecond-pulse-train ionization seed that is properly synchronized with the strong driving mid-infrared laser field can produce experimentally relevant high-harmonic generation (HHG) signals, from which we extract both the spectral amplitude and the target-specific phase (group delay). We also show that further processing of the HHG signal can be used to achieve molecular-frame resolution, i.e., to resolve the contributions from rescattering on different sides of an oriented molecule. In this framework, we investigate transient two-center interference in CO 2 and OCS, and how subcycle polarization effects shape the oriented/aligned angle-resolved spectra.
This study describes a novel series of UDP-N-acetylglucosamine acyltransferase (LpxA) inhibitors that was identified through affinity-mediated selection from a DNA-encoded compound library. The original hit was a selective inhibitor of Pseudomonas aeruginosa LpxA with no activity against Escherichia coli LpxA. The biochemical potency of the series was optimized through an X-ray crystallography-supported medicinal chemistry program, resulting in compounds with nanomolar activity against P. aeruginosa LpxA (best half-maximal inhibitory concentration (IC50) <5 nM) and cellular activity against P. aeruginosa (best minimal inhibitory concentration (MIC) of 4 μg/mL). Lack of activity against E. coli was maintained (IC50 > 20 μM and MIC > 128 μg/mL). The mode of action of analogues was confirmed through genetic analyses. As expected, compounds were active against multidrug-resistant isolates. Further optimization of pharmacokinetics is needed before efficacy studies in mouse infection models can be attempted. To our knowledge, this is the first reported LpxA inhibitor series with selective activity against P. aeruginosa.
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