A study of the ozonolysis of isoprene in a cryogenic buffer gas cell by high resolution microwave spectroscopy

We have developed a method to quantify reaction product ratios using high resolution microwave spectroscopy in a cryogenic buffer gas cell. We demonstrate the power of this method with the study of the ozonolysis of isoprene, CH2=C(CH3)-CH=CH2, the most abundant, non-methane hydrocarbon emitted into the atmosphere by vegetation. Isoprene is an asymmetric diene, and reacts with O3 at the 1,2 position to produce methyl vinyl ketone (MVK), formaldehyde, and a pair of carbonyl oxides: [CH3CO-CH=CH2 + CH2=OO] + [CH2=O + CH3COO-CH=CH2]. Alternatively, O3 could attack at the 3,4 position to produce methacrolein (MACR), formaldehyde, and two carbonyl oxides [CH2=C(CH3)-CHO + CH2=OO] + [CH2=O + CH2=C(CH3)-CHOO]. Purified O3 and isoprene were mixed for approximately 10 seconds under dilute (1.5-4% in argon) continuous flow conditions in an alumina tube held at 298 K and 5 Torr. Products exiting the tube were rapidly slowed and cooled within the buffer gas cell by collisions with cryogenic (4-7 K) He. High resolution chirped pulse microwave detection between 12 and 26 GHz was used to achieve highly sensitive (ppb scale), isomer-specific product quantification. We observed a ratio of MACR to MVK of 2.1 +/- 0.4 under 1:1 ozone to isoprene conditions and 2.1 +/- 0.2 under 2:1 ozone to isoprene conditions, a finding which is consistent with previous experimental results. Additionally, we discuss relative quantities of formic acid (HCOOH), an isomer of CH2=OO, and formaldehyde (CH2=O) under varying experimental conditions, and characterize the spectroscopic parameters of the singly-substituted 13C trans-isoprene and 13C anti-periplanar-methacrolein species. This work has the potential to be extended towards a complete branching ratio analysis, as well towards the ability to isolate, identify, and quantify new reactive intermediates in the ozonolysis of alkenes

HSCO+^+ and DSCO+^+: a multi-technique approach in the laboratory for the spectroscopy of interstellar ions

Protonated molecular species have been proven to be abundant in the interstellar gas. This class of molecules is also pivotal for the determination of important physical parameters for the ISM evolution (e.g. gas ionisation fraction) or as tracers of non-polar, hence not directly observable, species. The identification of these molecular species through radioastronomical observations is directly linked to a precise laboratory spectral characterisation. The goal of the present work is to extend the laboratory measurements of the pure rotational spectrum of the ground electronic state of protonated carbonyl sulfide (HSCO$^+$) and its deuterium substituted isotopomer (DSCO$^+$). At the same time, we show how implementing different laboratory techniques allows the determination of different spectroscopical properties of asymmetric-top protonated species. Three different high-resolution experiments were involved to detected for the first time the $b-$type rotational spectrum of HSCO$^+$, and to extend, well into the sub-millimeter region, the $a-$type spectrum of the same molecular species and DSCO$^+$. The electronic ground-state of both ions have been investigated in the 273-405 GHz frequency range, allowing the detection of 60 and 50 new rotational transitions for HSCO$^+$ and DSCO$^+$, respectively. The combination of our new measurements with the three rotational transitions previously observed in the microwave region permits the rest frequencies of the astronomically most relevant transitions to be predicted to better than 100 kHz for both HSCO$^+$ and DSCO$^+$ up to 500 GHz, equivalent to better than 60 m/s in terms of equivalent radial velocity. The present work illustrates the importance of using different laboratory techniques to spectroscopically characterise a protonated species at high frequency, and how a similar approach can be adopted when dealing with reactive species.Comment: 7 pages, 4 figures. Accepted for publication in Astronomy and Astrophysic

Vibrational Satellites of C2_2S, C3_3S, and C4_4S: Microwave Spectral Taxonomy as a Stepping Stone to the Millimeter-Wave Band

We present a microwave spectral taxonomy study of several hydrocarbon/CS$_2$ discharge mixtures in which more than 60 distinct chemical species, their more abundant isotopic species, and/or their vibrationally excited states were detected using chirped-pulse and cavity Fourier-transform microwave spectroscopies. Taken together, in excess of 85 unique variants were detected, including several new isotopic species and more than 25 new vibrationally excited states of C$_2$S, C$_3$S, and C$_4$S, which have been assigned on the basis of published vibration-rotation interaction constants for C$_3$S, or newly calculated ones for C$_2$S and C$_4$S. On the basis of these precise, low-frequency measurements, several vibrationally exited states of C$_2$S and C$_3$S were subsequently identified in archival millimeter-wave data in the 253--280 GHz frequency range, ultimately providing highly accurate catalogs for astronomical searches. As part of this work, formation pathways of the two smaller carbon-sulfur chains were investigated using $^{13}$C isotopic spectroscopy, as was their vibrational excitation. The present study illustrates the utility of microwave spectral taxonomy as a tool for complex mixture analysis, and as a powerful and convenient `stepping stone' to higher frequency measurements in the millimeter and submillimeter bands.Comment: Accepted in PCC

Models of the ICM with Heating and Cooling: Explaining the Global and Structural X-ray Properties of Clusters

(Abridged) Theoretical models that include only gravitationally-driven processes fail to match the observed mean X-ray properties of clusters. As a result, there has recently been increased interest in models in which either radiative cooling or entropy injection play a central role in mediating the properties of the intracluster medium. Both sets of models give reasonable fits to the mean properties of clusters, but cooling only models result in fractions of cold baryons in excess of observationally established limits and the simplest entropy injection models do not treat the "cooling core" structure present in many clusters and cannot account for entropy profiles revealed by recent X-ray observations. We consider models that marry radiative cooling with entropy injection, and confront model predictions for the global and structural properties of massive clusters with the latest X-ray data. The models successfully and simultaneously reproduce the observed L-T and L-M relations, yield detailed entropy, surface brightness, and temperature profiles in excellent agreement with observations, and predict a cooled gas fraction that is consistent with observational constraints. The model also provides a possible explanation for the significant intrinsic scatter present in the L-T and L-M relations and provides a natural way of distinguishing between clusters classically identified as "cooling flow" clusters and dynamically relaxed "non-cooling flow" clusters. The former correspond to systems that had only mild levels (< 300 keV cm^2) of entropy injection, while the latter are identified as systems that had much higher entropy injection. This is borne out by the entropy profiles derived from Chandra and XMM-Newton.Comment: 20 pages, 15 figures, accepted for publication in the Astrophysical Journa

What is psychosis? A meta-synthesis of inductive qualitative studies exploring the experience of psychosis

Qualitative studies have played an important role in elucidating the lived experience of psychosis and there has recently been an increase in the number of such studies. There is now an urgent need to draw together the findings of these studies. This paper performed a meta-synthesis of inductive qualitative peer-reviewed research into psychosis. Ninety-eight articles were identified for systematic appraisal. Four themes, ‘Losing’, ‘Identifying a need for, and seeking, help’, ‘Rebuilding and reforging’, and ‘Better than new: gifts from psychosis’, were identified. The important implications these themes for clinicians and future research are examined upon. These findings also highlight that the experience of psychosis is much more than simply just hallucinations and/or delusions

Improvements in X-Ray Spectrometry for Planetary Surface Exploration

Recent innovations in X-ray instrumentation have enabled a new generation of planetary XRS instruments exhibiting performance matching terr estrial laboratory results

Sulfur monoxide thermal release from an anthracene-based precursor, spectroscopic identification, and transfer reactivity

Sulfur monoxide (SO) is a highly reactive molecule and thus, eludes bulk isolation. We report here on synthesis and reactivity of a molecular precursor for SO generation, namely 7-sulfin-ylamino-7-azadibenzonorbornadiene (1). This compound has been shown to fragment readily driven by dinitrogen expulsion and anthracene formation on heating in the solid state and in solution, releasing SO at mild temperatures (<100 ◦C). The generated SO was detected in the gas phase by MS and rotational spectroscopy. In solution, 1 allows for SO transfer to organic molecules as well as transition metal complexes. Keywords: microwave spectroscopy; reactive intermediate; molecular precursor; astrochemistry; sulfur monoxid