Cyclobutadiene automerization and rotation of ethylene: Energetics of the barriers by using Spin-polarized wave functions

Spin-projected spin polarized Møller–Plesset and spin polarized coupled clusters calculations have been made to estimate the cyclobutadiene automerization, the ethylene torsion barriers in their ground state, and the gap between the singlet and triplet states of ethylene. The results have been obtained optimizing the geometries at MP4 and/or CCSD levels, by an extensive Gaussian basis set. A comparative analysis with more complex calculations, up to MP5 and CCSDTQP, together with others from the literature, have also been made, showing the efficacy of using spin-polarized wave functions as a reference wave function for Møller–Plesset and coupled clusters calculations, in such problems.

Modeling magnetar outbursts: flux enhancements and the connection with short bursts and glitches

The availability of a large amount of observational data recently collected from magnetar outbursts is now calling for a complete theoretical study of outburst characteristics. In this Letter (the first of a series dedicated to modeling magnetar outbursts), we tackle the long-standing open issue of whether or not short bursts and glitches are always connected to long-term radiative outbursts. We show that the recent detection of short bursts and glitches seemingly unconnected to outbursts is only misleading our understanding of these events. We show that, in the framework of the starquake model, neutrino emission processes in the magnetar crust limit the temperature, and therefore the luminosity. This natural limit to the maximum luminosity makes outbursts associated with bright persistent magnetars barely detectable. These events are simply seen as a small luminosity increase over the already bright quiescent state, followed by a fast return to quiescence. In particular, this is the case for 1RXS J1708–4009, 1E 1841–045, SGR 1806–20, and other bright persistent magnetars. On the other hand, a similar event (with the same energetics) in a fainter source will drive a more extreme luminosity variation and longer cooling time, as for sources such as XTE J1810–197, 1E 1547–5408, and SGR 1627–41. We conclude that the non-detection of large radiative outbursts in connection with glitches and bursts from bright persistent magnetars is not surprising per se, nor does it need any revision of the glitches and burst mechanisms as explained by current theoretical models.

Interplay Between Structure, Stoichiometry, and Electron Transfer Dynamics in SILAR-based Quantum Dot-Sensitized Oxides

We quantify the rate and efficiency of picosecond electron transfer (ET) from PbS nanocrystals, grown by successive ionic layer adsorption and reaction (SILAR), into a mesoporous SnO2 support. Successive SILAR deposition steps allow for stoichiometry- and size-variation of the QDs, characterized using transmission electron microscopy. Whereas for sulfur-rich (p-type) QD surfaces substantial electron trapping at the QD surface occurs, for lead-rich (n-type) QD surfaces, the QD trapping channel is suppressed and the ET efficiency is boosted. The ET efficiency increase achieved by lead-rich QD surfaces is found to be QD-size dependent, increasing linearly with QD surface area. On the other hand, ET rates are found to be independent of both QD size and surface stoichiometry, suggesting that the donor–acceptor energetics (constituting the driving force for ET) are fixed due to Fermi level pinning at the QD/oxide interface. Implications of our results for QD-sensitized solar cell design are discussed.