Chemical physics and astrochemistry of H3+ and sub Doppler mid infrared spectroscopy of molecular ions

Molecular ions are known to be key reactive intermediates in interstellar environments, and H3+ in particular is responsible for initiating a network of chemical reactions that ultimately results in the formation of the ~170 molecules detected so far in space. Yet fundamental questions about the interstellar abundances of the two nuclear spin configurations of H3+ (ortho-H3+, I=3/2; and para-H3+, I=1/2) remain. In this thesis, experiments to measure the nuclear spin dependence of the chemical reactions of H3+ with electrons and with molecular hydrogen at astronomically relevant temperatures are described. The results of these laboratory measurements are included into a model of the hydrogenic chemistry of diffuse molecular clouds, in which an excess of para-H3+ is observed relative to its expected abundance at the measured cloud temperature. The model suggests that the ortho:para ratio is likely controlled by a competition between the aforementioned chemical reactions of H3+ with electrons and molecular hydrogen. Other molecular ions may similarly be useful for constraining the physical and chemical conditions of astronomical environments, but such insight can only be derived if laboratory spectroscopy of these ions has been performed. However, for many ionic species, insufficient laboratory data are available, and this is primarily because of difficulties in producing sufficient quantities of ions for traditional spectroscopic techniques. This thesis discusses the development of instrumentation to overcome the challenge of ion production. First, a continuous supersonic expansion discharge source is described that allows for the production of internally cold molecular ions in modest abundance, thereby maximizing population in the lowest-lying energy states relevant for astronomical spectroscopy. Then, an instrument for performing sub-Doppler spectroscopy of molecular ions in a liquid nitrogen cooled plasma is discussed. This instrument offers ultra high sensitivity, and sufficient accuracy and precision that rotational frequencies suitable for observational astronomy can be inferred. As a case study of the performance and capabilities of this instrument, the high resolution sub-Doppler spectrum of H3+ is presented

A Laboratory Study of C_3H^+ and the C_3H Radical in Three New Vibrationally Excited ^2Σ States Using a Pin-Hole Nozzle Discharge Source

Rotational lines of the positive molecular ion C_3H^+ and of the neutral C_3H radical in three new vibrationally excited states with ^2Σ symmetry have been detected in a supersonic molecular beam in the centimeter-wave band. The fundamental rotational line of the ion is quite weak, but is observed with similar intensity in a dc discharge through several different hydrocarbon gases when helium is the buffer gas. Under these conditions, the fractional abundance of C_3H^+ relative to C_3H is estimated to be of order 10^(−4), i.e., toward the lower end of the ratio (10^(−3)–10^(−4)) found for protonated ions using the same discharge nozzle. For each new ^2Σ state of the C_3H radical, spectroscopic constants, including those describing hydrogen hyperfine structure, have been determined to high precision. Lines of one ^2Σ state (B = 11271 MHz) are particularly intense in our molecular beam; for this state and a second one (B = 11306 MHz), millimeter-wave transitions have also been observed between 180 and 340 GHz using a long path dc glow absorption spectrometer. On the basis of intensity measurements with this spectrometer, the inferred rotation–vibration constant α, and theoretical calculations, the state with B = 11271 MHz is tentatively assigned to the ν_5 bending mode, predicted to lie ~300 cm^(−1) above ground

Ab initio Study of Ground-State CS Photodissociation Via Highly Excited Electronic States

Photodissociation by ultraviolet radiation is the key destruction pathway for CS in photon-dominated regions, such as diffuse clouds. However, the large uncertainties of photodissociation cross sections and rates of CS, resulting from a lack of both laboratory experiments and theoretical calculations, limit the accuracy of calculated abundances of S-bearing molecules by modern astrochemical models. Here we show a detailed \textit{ab initio} study of CS photodissociation. Accurate potential energy curves of CS electronic states were obtained by choosing an active space CAS(8,10) in MRCI+Q/aug-cc-pV(5+d)Z calculation with additional diffuse functions, with a focus on the $B$ and C\,^1\Sigma^+ states. Cross sections for both direct photodissociation and predissociation from the vibronic ground state were calculated by applying the coupled-channel method. We found that the $C-X$ $(0-0)$ transition has extremely strong absorption due to a large transition dipole moment in the Franck-Condon region and the upper state is resonant with several triplet states via spin-orbit couplings, resulting in predissociation to the main atomic products C $(^3P)$ and S $(^1D)$. Our new calculations show the photodissociation rate under the standard interstellar radiation field is 2.9\ee{-9}\,s$^{-1}$, with a 57\% contribution from $C-X$ $(0-0)$ transition. This value is larger than that adopted by the Leiden photodissociation and photoionization database by a factor of 3.0. Our accurate \textit{ab initio} calculations will allow more secure determination of S-bearing molecules in astrochemical models.Comment: 23 pages, 14 figure

Interaction Between the Broad-Lined Type Ic Supernova 2012ap and Carriers of Diffuse Interstellar Bands

Diffuse interstellar bands (DIBs) are absorption features observed in optical and near-infrared spectra that are thought to be associated with carbon-rich polyatomic molecules in interstellar gas. However, because the central wavelengths of these bands do not correspond to electronic transitions of any known atomic or molecular species, their nature has remained uncertain since their discovery almost a century ago. Here we report on unusually strong DIBs in optical spectra of the broad-lined Type Ic supernova SN 2012ap that exhibit changes in equivalent width over short ( 30 days) timescales. The 4428 Å and 6283 Å DIB features get weaker with time, whereas the 5780 Å feature shows a marginal increase. These nonuniform changes suggest that the supernova is interacting with a nearby source of DIBs and that the DIB carriers possess high ionization potentials, such as small cations or charged fullerenes. We conclude that moderate-resolution spectra of supernovae with DIB absorptions obtained within weeks of outburst could reveal unique information about the mass-loss environment of their progenitor systems and provide new constraints on the properties of DIB carriers

On the Ortho:Para Ratio of H3+ in Diffuse Molecular Clouds

The excitation temperature T_01 derived from the relative intensities of the J = 0 (para) and J = 1 (ortho) rotational levels of H2 has been assumed to be an accurate measure of the kinetic temperature in interstellar environments. In diffuse molecular clouds, the average value of T_01 is ~70 K. However, the excitation temperature T(H3+) derived from the (J,K) = (1,1) (para) and (1,0) (ortho) rotational levels of H3+ has been observed to be ~30 K in the same types of environments. In this work, we present observations of H3+ in three additional diffuse cloud sight lines for which H2 measurements are available, showing that in 4 of 5 cases T_01 and T(H3+) are discrepant. We then examine the thermalization mechanisms for the ortho:para ratios of H3+ and H2, concluding that indeed T_01 is an accurate measure of the cloud kinetic temperature, while the ortho:para ratio of H3+ need not be thermal. By constructing a steady-state chemical model taking into account the nuclear-spindependence of reactions involving H3+, we show that the ortho:para ratio of H3+ in diffuse molecular clouds is likely governed by a competition between dissociative recombination with electrons and thermalization via reactive collisions with H2.Comment: 13 pages, 8 figures, 5 tables, accepted for publication in Ap

Interaction Between the Broad-Lined Type Ic Supernova 2012ap and Carriers of Diffuse Interstellar Bands

The diffuse interstellar bands (DIBs) are absorption features observed in optical and near-infrared spectra that are thought to be associated with carbon-rich polyatomic molecules in interstellar gas. However, because the central wavelengths of these bands do not correspond with electronic transitions of any known atomic or molecular species, their nature has remained uncertain since their discovery almost a century ago. Here we report on unusually strong DIBs in optical spectra of the broad- lined Type Ic supernova SN2012ap that exhibit changes in equivalent width over short (. 30 days) timescales. The 4428 A and 6283 A DIB features get weaker with time, whereas the 5780 A feature shows a marginal increase. These nonuniform changes suggest that the supernova is interacting with a nearby source of the DIBs and that the DIB carriers possess high ionization potentials, such as small cations or charged fullerenes. We conclude that moderate-resolution spectra of supernovae with DIB absorptions obtained within weeks of outburst could reveal unique information about the mass-loss environment of their progenitor systems and provide new constraints on the properties of DIB carriers

X-ray absorption spectroscopy systematics at the tungsten L-edge

A series of mononuclear six-coordinate tungsten compounds spanning formal oxidation states from 0 to +VI, largely in a ligand environment of inert chloride and/or phosphine, has been interrogated by tungsten L-edge X-ray absorption spectroscopy. The L-edge spectra of this compound set, comprised of [W<sup>0</sup>(PMe<sub>3</sub>)<sub>6</sub>], [W<sup>II</sup>Cl<sub>2</sub>(PMePh<sub>2</sub>)<sub>4</sub>], [W<sup>III</sup>Cl<sub>2</sub>(dppe)<sub>2</sub>][PF<sub>6</sub>] (dppe = 1,2-bis(diphenylphosphino)ethane), [W<sup>IV</sup>Cl<sub>4</sub>(PMePh<sub>2</sub>)<sub>2</sub>], [W<sup>V</sup>(NPh)Cl<sub>3</sub>(PMe<sub>3</sub>)<sub>2</sub>], and [W<sup>VI</sup>Cl<sub>6</sub>] correlate with formal oxidation state and have usefulness as references for the interpretation of the L-edge spectra of tungsten compounds with redox-active ligands and ambiguous electronic structure descriptions. The utility of these spectra arises from the combined correlation of the estimated branching ratio (EBR) of the L<sub>3,2</sub>-edges and the L<sub>1</sub> rising-edge energy with metal Z<sub>eff</sub>, thereby permitting an assessment of effective metal oxidation state. An application of these reference spectra is illustrated by their use as backdrop for the L-edge X-ray absorption spectra of [W<sup>IV</sup>(mdt)<sub>2</sub>(CO)<sub>2</sub>] and [W<sup>IV</sup>(mdt)<sub>2</sub>(CN)<sub>2</sub>]<sup>2–</sup> (mdt<sup>2–</sup> = 1,2-dimethylethene-1,2-dithiolate), which shows that both compounds are effectively W<sup>IV</sup> species. Use of metal L-edge XAS to assess a compound of uncertain formulation requires: 1) Placement of that data within the context of spectra offered by unambiguous calibrant compounds, preferably with the same coordination number and similar metal ligand distances. Such spectra assist in defining upper and/or lower limits for metal Z<sub>eff</sub> in the species of interest; 2) Evaluation of that data in conjunction with information from other physical methods, especially ligand K-edge XAS; 3) Increased care in interpretation if strong π-acceptor ligands, particularly CO, or π-donor ligands are present. The electron-withdrawing/donating nature of these ligand types, combined with relatively short metal-ligand distances, exaggerate the difference between formal oxidation state and metal Z<sub>eff</sub> or, as in the case of [W<sup>IV</sup>(mdt)<sub>2</sub>(CO)<sub>2</sub>], add other subtlety by modulating the redox level of other ligands in the coordination sphere

National identity predicts public health support during a global pandemic (vol 13, 517, 2022) : National identity predicts public health support during a global pandemic (Nature Communications, (2022), 13, 1, (517), 10.1038/s41467-021-27668-9)

Publisher Copyright: © The Author(s) 2022.In this article the author name ‘Agustin Ibanez’ was incorrectly written as ‘Augustin Ibanez’. The original article has been corrected.Peer reviewe

National identity predicts public health support during a global pandemic.

Changing collective behaviour and supporting non-pharmaceutical interventions is an important component in mitigating virus transmission during a pandemic. In a large international collaboration (Study 1, N = 49,968 across 67 countries), we investigated self-reported factors associated with public health behaviours (e.g., spatial distancing and stricter hygiene) and endorsed public policy interventions (e.g., closing bars and restaurants) during the early stage of the COVID-19 pandemic (April-May 2020). Respondents who reported identifying more strongly with their nation consistently reported greater engagement in public health behaviours and support for public health policies. Results were similar for representative and non-representative national samples. Study 2 (N = 42 countries) conceptually replicated the central finding using aggregate indices of national identity (obtained using the World Values Survey) and a measure of actual behaviour change during the pandemic (obtained from Google mobility reports). Higher levels of national identification prior to the pandemic predicted lower mobility during the early stage of the pandemic (r = -0.40). We discuss the potential implications of links between national identity, leadership, and public health for managing COVID-19 and future pandemics