1,864 research outputs found

    Kasha’s Rule and Koopmans’ Correlations for Electron Tunnelling through Repulsive Coulomb Barriers in a Polyanion

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    The long-range electronic structure of polyanions is defined by the repulsive Coulomb barrier (RCB). Excited states can decay by resonant electron tunnelling through RCBs, but such decay has not been observed for electronically excited states other than the first excited state, suggesting a Kasha-type rule for resonant electron tunnelling. Using action spectroscopy, photoelectron imaging, and computational chemistry, we show that the fluorescein dianion, Fl2–, partially decays through electron tunnelling from the S2 excited state, thus demonstrating anti-Kasha behavior, and that resonant electron tunnelling adheres to Koopmans’ correlations, thus disentangling different channels

    A new 1.6-micron map of Titan’s surface

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    We present a new map of Titan's surface obtained in the spectral 'window' at ∼1.6 μm between strong methane absorption. This pre-Cassini view of Titan's surface was created from images obtained using adaptive optics on the W.M. Keck II telescope and is the highest resolution map yet made of Titan's surface. Numerous surface features down to the limits of the spatial resolution (∼200–300 km) are apparent. No features are easily identifiable in terms of their geologic origin, although several are likely craters

    Photoelectron spectroscopy of the deprotonated tryptophan anion: the contribution of deprotomers to its photodetachment channels †

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    Photoelectron spectroscopy and electronic structure calculations are used to investigate the electronic structure of the deprotonated anionic form of the aromatic amino acid tryptophan, and its chromophore, indole. The photoelectron spectra of tryptophan, recorded at different wavelengths across the UV, consist of two direct detachment channels and thermionic emission, whereas the hν = 4.66 eV spectrum of indole consists of two direct detachment features. Electronic structure calculations indicate that two deprotomers of tryptophan are present in the ion beam; deprotonation of the carboxylic acid group (Trp(i)−) or the N atom on the indole ring (Trp(ii)−). Strong similarities are observed between the direct detachment channels in the photoelectron spectra of tryptophan and indole, which in conjunction with electronic structure calculations, indicate that electron loss from Trp(ii)− dominates this portion of the spectra. However, there is some evidence that direct detachment of Trp(i)− is also observed. Thermionic emission is determined to predominantly arise from the decarboxylation of Trp(i)−, mediated by the ππ* excited state near λ = 300 nm, which results in an anionic fragment with a negative electron affinity that readily autodetaches

    Association of prenatal alcohol exposure and offspring depression:A negative control analysis of maternal and partner consumption

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    Background: Previous research has suggested that intrauterine alcohol exposure is associated with a variety of adverse outcomes in offspring. However, few studies have investigated its association with offspring internalizing disorders in late adolescence. Methods: Using data from the Avon Longitudinal Study of Parents and Children (ALSPAC), we investigated the associations of maternal drinking in pregnancy with offspring depression at age 18 and 24 (n=13,480). We also examined partner drinking as a negative control for intrauterine exposure for comparison. Results: Offspring of mothers that consumed any alcohol at 18weeks gestation were at increased risk of having a diagnosis of depression (fully adjusted model: OR 1.17, 95% CI 1.02 to 1.34), but there was no clear evidence of association between partners’ alcohol consumption at 18weeks gestation during pregnancy and increased risk of offspring depression (fully adjusted model: OR 0.87, 95% CI 0.74 to 1.01). Postestimation tests found a positive difference between the association of maternal and partner alcohol use on offspring depression, showing a stronger association for maternal compared with partner alcohol use (OR 1.41, CI 1.07 to 1.84). Conclusions: Maternal drinking in pregnancy was associated with increased risk of offspring depression at age 18. Residual confounding may explain this association, but the negative control comparison of paternal drinking provides some evidence that it may be causal, and this warrants further investigation

    Inclusion of higher order terms for small-signal (modal) analysis: Committee report - task force on assessing the need to include higher order terms for small-signal (modal) analysis

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    © 2005 IEEE.This paper summarizes the work done by the Task Force on Assessing the Need to Include Higher Order Terms for Small-Signal (Modal) Analysis. This Task Force was created by the Power System Dynamic Performance Committee to investigate the need to include higher order terms for small signal (modal) analysis. The focus of the work reported here is on establishing and documenting the practical significance of these terms in stability analysis using the method of Normal Forms. Special emphasis was placed on determining and describing conditions when higher order terms need to be included to accurately describe modal interactions. Test cases were developed on a standard test system to demonstrate the application of appropriate indices to detect the occurrence of nonlinear interaction and hence the need for higher order terms in stability analyzes. The use of the higher order terms in the site selection for a damping controller is also documented.Sanchez-Gasca, Juan J.,Vittal, Vijay; Gibbard, Michael J.; Messina, Arturo Roman; Vowles, David J.; Liu, Shu; Annakkage, Udaya D
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