Vibrationally resolved rate coefficients and branching fractions in the dissociative recombination of O2+

We have studied the dissociative recombination of the first three vibrational levels of O(2) (+) in its electronic ground X (2)Pi(g) state. Absolute rate coefficients, cross sections, quantum yields and branching fractions have been determined in a merged-beam experiment in the heavy-ion storage ring, CRYRING, employing fragment imaging for the reaction dynamics. We present the absolute total rate coefficients as function of collision energies up to 0.4 eV for five different vibrational populations of the ion beam, as well as the partial (vibrationally resolved) rate coefficients and the branching fractions near 0 eV collision energy for the vibrational levels v=0, 1, and 2. The vibrational populations used were produced in a modified electron impact ion source, which has been calibrated using Cs-O(2)(+) dissociative charge transfer reactions. The measurements indicate that at low collision energies, the total rate coefficient is weakly dependent on the vibrational excitation. The calculated thermal rate coefficient at 300 K decreases upon vibrational excitation. The partial rate coefficients as well as the partial branching fractions are found to be strongly dependent on the vibrational level. The partial rate coefficient is the fastest for v=0 and goes down by a factor of two or more for v=1 and 2. The O((1)S) quantum yield, linked to the green airglow, increases strongly upon increasing vibrational level. The effects of the dissociative recombination reactions and super elastic collisions on the vibrational populations are discussed.     

High-resolution photofragment spectroscopy of the O2+b4Σg− (v′ = 3, 4, 5) ← a4Πu (v′ = 3, 4, 5) First Negative system using coaxial dye-laser and velocity-tuned ion beams

A new photofragment spectrometer employing coaxial tunable single-mode laser and velocity-tuned fast-ion beams has been used to measure transition energies in the O₂⁺b⁴Σ_g^? ← a⁴Π_u First Negative system to an accuracy and precision that are an order of magnitude better than was previously possible in Doppler-limited emission spectroscopy. The technique consists of velocity-tuning a beam of metastable O₂⁺a⁴Π_u ions such that a set of First Negative rotational transitions can be sequentially brought into resonance with the laser wavelength. The subsequent absorption transitions promote the ions to predissociating levels of the b⁴Σ_g^? state and observation of the O⁺ photofragments is the signal that denotes that each absorption transition has occurred. Repetition of the velocity tuning at different dye-laser frequencies provides a scan of the First Negative spectrum for predissociating upper-state vibrational levels, which are inaccessible to emission spectroscopy. The O⁺ photofragment ions have a kinetic energy that depends on the height of the predissociating rotational level above the separatedatom limit. The present apparatus incorporates a photofragment energy analyzer that can often be used to separately record the wavenumbers of transitions to different upper-state rotational levels, but whose wavenumbers could not otherwise be resolved. A set of 359 wavenumbers involving the (4,4), (4,5), (5,5), and (3,3) bands were recorded with an estimated accuracy of ±0.0032 cm^?1 and a precision of 0.0028 cm^?1, the latter being estimated precisely with a statistical technique. These data were fitted to ⁴Σ and ⁴Π Hamiltonians used in recent studies of the First Negative emission spectrum to determine molecular constants for the v′ = 4, 5 and v″ = 4, 5 levels. The former represent an extension of the b⁴Σ_g^? state to new levels and the latter represent substantial improvements over the constants that were available from previous moderate-resolution emission studies. These photofragment molecular constants were merged with those from the previous emission studies to yield a new consistent set of molecular constants and Dunham coefficients for the O₂⁺b⁴Σ_g^? and a⁴Π_u states. In the fit to the photofragment bands, it was found that the Hamiltonians, which were sufficient for the emission data, are inadequate to describe these states within the precision of the present measurements.     

ESI‐MS/MS of expanded porphyrins: a look into their structure and aromaticity

Electrospray mass spectrometry/mass spectrometry was used to investigate the gas‐phase properties of protonated expanded porphyrins, in order to correlate those with their structure and conformation. We have selected five expanded meso‐pentafluorophenyl porphyrins, respectively, a pair of oxidized/reduced fused pentaphyrins (22 and 24 π electrons), a pair of oxidized/reduced regular hexaphyrins (26 and 28 π electrons) and a regular doubly N‐fused hexaphyrin (28 π electrons). The gas‐phase behavior of the protonated species of oxidized and reduced expanded porphyrins is different. The oxidized species (aromatic Hückel systems) fragment more extensively, mainly by the loss of two HF molecules. The reduced species (Möbius aromatic or Möbius‐like aromatic systems) fragment less than their oxidized counterparts because of their increased flexibility. The protonated regular doubly fused hexaphyrin (non‐aromatic Hückel system) shows the least fragmentation even at higher collision energies. In general, cyclization through losses of HF molecules decreases from the aromatic Hückel systems to Möbius aromatic or Möbius‐like aromatic systems to non‐aromatic Hückel systems and is related to an increase in conformational distortion. Copyright © 2016 John Wiley & Sons, Ltd.