On the Electronic Spectroscopy of Closed Shell Cations Derived From Resonance Stabilized Radicals: Insights From Theory and Franck-Condon Analysis

Context. Recent attention has been directed on closed-shell aromatic cations as potential carriers of the diffuse interstellar bands. The spectra of mass-selected, matrix-isolated benzylium, and tropylium cations were recently reported. The visible spectrum of benzylium exhibits a large Franck-Condon (FC) envelope, inconsistent with diffuse interstellar band carriers. Aims. We perform a computational analysis of the experimentally studied benzylium spectrum before extending the methods to a range of larger, closed-shell aromatic cations to determine the potential for this class of systems as diffuse interstellar band carriers. Methods. Density functional theory (DFT), time-dependant ((TD)DFT), and multi-configurational self-consistent field second-order perturbation theory (MRPT2) methods in concert with multidimensional FC analysis is used to model the benzylium spectrum. These methods are extended to larger closed-shell aromatic hydrocarbon cations derived from resonance-stabilized radicals, which are predicted to show strong S0 → Sn transitions in the visible region. The ionization energies of a range of these systems are also calculated by DFT. Results. The simulated benzylium spectrum was found to yield excellent agreement with the experimental spectrum showing an extended progression in a low frequency (510 cm-1) ring distortion mode. The FC progression was found to be significantly quenched in the larger species: 1-indanylium, 1-naphthylmethylium, and fluorenium. Excitation and ionization energies of the closed-shell cations were found to be consistent with diffuse interstellar band carriers, with the former lying in the visible range and the latter straddling the Lyman limit in the 13−14 eV range. Conclusions. Large closed-shell polycyclic aromatic hydrocarbon cations remain viable candidate carriers of the diffuse interstellar bands

No new limit on the size distribution of gamma-ray bursts

The results of a study (Carter et. al.) of gamma ray bursts using long duration balloon exposure are analyzed. Arguments are presented against the conclusion that the size spectrum extrapolates to a power law with index from -1.0 to -0.5, and that therefore the gamma ray bursts are of galactic origin. It is claimed that the data are consistent with an upper limit over 100 times that proposed, and that therefore no conclusion can be drawn from the measurements regarding the nature or origin of gamma ray bursts. The resulting upper limit to the rate of occurrence of small bursts lies above the -1.5 index power law extrapolation of the size spectrum of known events, i.e., greater than the rate expected from an infinitely extended source region

ZZE-Configuration of chromophore ß-153 in C-phycocyanin from Mastigocladus laminosus

The photochemistry of C-phycocyanin has been studied after denaturation in the dark. It shows an irreversible reaction which has characteristics of a Ζ,Ζ,Ε- to Z,Z,Z-isomerization of dihydrobilins. Its amplitude depends on the reaction conditions, with a maximum corresponding to 15% conversion of one of the three PC chromophores. This chromophore is suggested to be ß-153, for which recent X-ray data T. Schirmer, W. Bode, and R. Huber, J. Mol. Biol., submitted, show ring D being highly twisted out of the plane of the other rings. During unfolding, there is thus a probability of falling into the photochemically labile Z,Z,^-configuration

Comment on 'Stability of the semiclassical Einstein equation'

Some mathematical errors of the paper commented upon [W.-M. Suen, Phys. Rev. D 40, (1989) 315] are corrected.Comment: 3 pages, LaTeX, reprinted from Phys. Rev. D 50 (1994) 545

Voltage-Controlled Spin Selection in a Magnetic Resonant Tunnelling Diode

We have fabricated all II-VI semiconductor resonant tunneling diodes based on the (Zn,Mn,Be)Se material system, containing dilute magnetic material in the quantum well, and studied their current-voltage characteristics. When subjected to an external magnetic field the resulting spin splitting of the levels in the quantum well leads to a splitting of the transmission resonance into two separate peaks. This is interpreted as evidence of tunneling transport through spin polarized levels, and could be the first step towards a voltage controlled spin filter.Comment: To be published in Phys. Rev. Let

Comb-calibrated solar spectroscopy through a multiplexed single-mode fiber channel

We investigate a new scheme for astronomical spectrograph calibration using the laser frequency comb at the Solar Vacuum Tower Telescope on Tenerife. Our concept is based upon a single-mode fiber channel, that simultaneously feeds the spectrograph with comb light and sunlight. This yields nearly perfect spatial mode matching between the two sources. In combination with the absolute calibration provided by the frequency comb, this method enables extremely robust and accurate spectroscopic measurements. The performance of this scheme is compared to a sequence of alternating comb and sunlight, and to absorption lines from Earth's atmosphere. We also show how the method can be used for radial-velocity detection by measuring the well-explored 5-minute oscillations averaged over the full solar disk. Our method is currently restricted to solar spectroscopy, but with further evolving fiber-injection techniques it could become an option even for faint astronomical targets.Comment: 21 pages, 11 figures. A video abstract for this paper is available on youtube. For watching the video, please follow https://www.youtube.com/watch?v=oshdZgrt89I . The video abstract is also available for streaming and download on the related article website of New Journal of Physic