Ultraviolet photodissociation action spectroscopy of the N-pyridinium cation

© 2015 AIP Publishing LLC. The S1←S0 electronic transition of the N-pyridinium ion (C5H5NH+) is investigated using ultraviolet photodissociation (PD) spectroscopy of the bare ion and also the N2-tagged complex. Gas-phase N-pyridinium ions photodissociate by the loss of molecular hydrogen (H2) in the photon energy range 37 000-45 000 cm-1 with structurally diagnostic ion-molecule reactions identifying the 2-pyridinylium ion as the exclusive co-product. The photodissociation action spectra reveal vibronic details that, with the aid of electronic structure calculations, support the proposal that dissociation occurs through an intramolecular rearrangement on the ground electronic state following internal conversion. Quantum chemical calculations are used to analyze the measured spectra. Most of the vibronic features are attributed to progressions of totally symmetric ring deformation modes and out-of-plane modes active in the isomerization of the planar excited state towards the non-planar excited state global minimum

Electronic absorptions of the benzylium cation

C1 - Journal Articles RefereedThe electronic transitions of the benzylium cation (Bz(+)) are investigated over the 250-550 nm range by monitoring the photodissociation of mass-selected C(7)H(7)(+)-Ar(n) (n = 1, 2) complexes in a tandem mass spectrometer. The Bz(+)-Ar spectrum displays two distinct band systems, the S(1)←S(0) band system extending from 370 to 530 nm with an origin at 19,067 ± 15 cm(-1), and a much stronger S(3)←S(0) band system extending from 270 to 320 nm with an origin at 32,035 ± 15 cm(-1). Whereas the S(1)←S(0) absorption exhibits well resolved vibrational progressions, the S(3)←S(0) absorption is broad and relatively structureless. Vibronic structure of the S(1)←S(0) system, which is interpreted with the aid of time-dependent density functional theory and Franck-Condon simulations, reflects the activity of four totally symmetric ring deformation modes (ν(5), ν(6), ν(9), ν(13)). We find no evidence for the ultraviolet absorption of the tropylium cation, which according to the neon matrix spectrum should occur over the 260 - 275 nm range [A. Nagy, J. Fulara, I. Garkusha, and J. Maier, Angew. Chem., Int. Ed. 50, 3022 (2011)]

The spectroscopy and thermochemistry of phenylallyl radical chromophores

The resonant two-color two-photon ionization and laser induced fluorescence excitation spectra of the 1-phenylallyl (cinnamyl) and inden-2-ylmethyl radicals are reported. The 1-phenylallyl radical is found to fluoresce with low yield, permitting only a coarse dispersed fluorescence spectrum, while the inden-2-ylmethyl radical yields sufficient fluorescence to obtain ground-state vibrational frequencies and two-dimensional fluorescence spectra. Computed ionization energies and thermochemical properties including radical stabilization energies are reported for a range of resonance-stabilized radicals, including the phenylpropargyl, vinylpropargyl and phenylallyl radicals

Caterpillar performance data

This csv files contains the larval performance data for the Lycaeides melissa caterpillars. Metrics include 8 and 16 day weight, pupal weight, and pupation and eclosion dates (which were used to compute survival to pupation/eclosion). Caterpillar IDs and Medicago truncatula plant lines are given

THE GAS-PHASE SPECTRA OF RESONANCE-STABILIZED RADICALS AND THE RED RECTANGLE EMISSION

Author Institution: School of Chemistry, The University of Sydney, NSW 2006, AustraliaAlpha aromatic radicals may explain some of the emission features of Red Rectangle (RR), a nearby protoplanetary nebulae. Erosion of amorphous hydrogenated carbon may lead to resonance-stabilized products by breaking aliphatic side-chains to aromatic ``islands''. The resulting radicals may be excited by starlight to give rise to the characteristic emissions. As a part of the ongoing research nderline{\textbf{130}}(10), 3137 (2009).} nderline{\textbf{113}}, 10279 (2009).} and in order to investigate this hypothesis, the gas-phase excitation and emission spectra of some of these radicals have been identified in a molecular beam using laser induced fluorescence (LIF) spectroscopy. Resonance-stabilized 1-naphthylmethyl, 2-naphthylmethyl and acenaphthenyl radicals were produced from the discharge of 1-methylnaphthalene, 2-methylnaphthalene and acenaphthene precursors in argon, respectively. In order to determine the ground state vibrational energies of these species, their fluorescence bands were dispersed. The results are consistent with the Density Functional Theory (DFT) calculated ground state frequencies. As a complementary experiment, and to further confirm the identity of the spectral carriers, resonant two color two photon ionization (R2C2PI) spectra were also recorded. The origin bands of all these three molecules show up in the 5790 - 5840\,{\AA} range of the spectrum, the well-known RR emission region

Genomic estimated breeding values

This compressed directory contains three text files with genomic estimated breeding values (GEBVs) for each line and trait. GEBVs for chemistry, caterpillar and plant traits are in bv_pred_ir.txt, bv_pred_cat.txt and bv_pred_plant.txt, respectively

IR chemistry data

This csv file provides IR transmittance values for each Medicago truncatula line and replicate for each of 58 IR chemical features