Oxygen isotopic composition of carbon dioxide in the middle atmosphere

The isotopic composition of long-lived trace molecules provides a window into atmospheric transport and chemistry. Carbon dioxide is a particularly powerful tracer, because its abundance remains >100 parts per million by volume (ppmv) in the mesosphere. Here, we successfully reproduce the isotopic composition of CO2 in the middle atmosphere, which has not been previously reported. The mass-independent fractionation of oxygen in CO2 can be satisfactorily explained by the exchange reaction with O(1D). In the stratosphere, the major source of O(1D) is O3 photolysis. Higher in the mesosphere, we discover that the photolysis of 16O17O and 16O18O by solar Lyman-{alpha} radiation yields O(1D) 10–100 times more enriched in 17O and 18O than that from ozone photodissociation at lower altitudes. This latter source of heavy O(1D) has not been considered in atmospheric simulations, yet it may potentially affect the "anomalous" oxygen signature in tropospheric CO2 that should reflect the gross carbon fluxes between the atmosphere and terrestrial biosphere. Additional laboratory and atmospheric measurements are therefore proposed to test our model and validate the use of CO2 isotopic fractionation as a tracer of atmospheric chemical and dynamical processes

Excited states of atmospheric molecules: spectra, structures and interactions : a thesis submitted for the degree of Doctor of Science of the University of Adelaide / Brenton R. Lewis.

Includes bibliographical references.1 v. :Title page, contents and abstract only. The complete thesis in print form is available from the University Library.The experimental, analytical and computational research achievements of the author, relating to the study of the interaction of vacuum ultraviolet radiation with molecules of particular atmospheric, aeronomic, or astrophysical significance are described. Elucidates details of molecular structure and dynamics through comparision between precise experimental measurements and quantum-mechanical calculations, and provides benchmark experimental molecular data and develops molecular modelling techniques intended to contribute to the solution of problems in the photochemistry of the terrestial and planetary atmospheres, aeronomy and astrophysicsThesis (D.Sc.)--University of Adelaide, Dept. of Physics and Mathematical Physics, 200

Photodissociation of interstellar N2

Molecular nitrogen is one of the key species in the chemistry of interstellar clouds and protoplanetary disks and the partitioning of nitrogen between N and N2 controls the formation of more complex prebiotic nitrogen-containing species. The aim of this work is to gain a better understanding of the interstellar N2 photodissociation processes based on recent detailed theoretical and experimental work and to provide accurate rates for use in chemical models. We simulated the full high-resolution line-by-line absorption + dissociation spectrum of N2 over the relevant 912-1000 \AA\ wavelength range, by using a quantum-mechanical model which solves the coupled-channels Schr\"odinger equation. The simulated N2 spectra were compared with the absorption spectra of H2, H, CO, and dust to compute photodissociation rates in various radiation fields and shielding functions. The effects of the new rates in interstellar cloud models were illustrated for diffuse and translucent clouds, a dense photon dominated region and a protoplanetary disk.Comment: Online database: http://home.strw.leidenuniv.nl/~ewine/phot

Analysis of terrestrial thermospheric N2c′41Σ+u(0) ~ b′1Σ+u(1)- X1Σ+g dayglow emission observed by the Far Ultraviolet Spectroscopic Explorer

Terrestrial thermospheric dayglow emission from the coupled and overlapping c′41Σ+u(0) and b′1Σ+u(1) levels of molecular nitrogen, observed by the Far Ultraviolet Spectroscopic Explorer, is analyzed with the aid of a coupled channels quantum mechanical model of N2 spectroscopy and predissociation dynamics. Model emission spectra for the mixed c′41Σ+u(0) ~ b′1Σ+u(1) − X1Σ+g(vi = 2, 6–9) transitions, calculated for the case of excitation by photoelectron impact, are in excellent agreement with the observations. While the principal excitation mechanism for N2 in the thermosphere is photoelectron impact, evidence is also found in other transitions of resonant fluorescence, induced by lines in the solar atomic hydrogen Lyman series, atomic oxygen transitions, and other N2 bands. The observed emission rate of the c′41Σ+u(0)~ b′1Σ+u(1)− X1Σ+(0) band is ~1% of that inferred from the emission rates to X1Σ+g(vi > 2) levels. A qualitative explanation is given for the drastically reduced intensity and band shape distortion observed in the c′41Σ+u(0)− X1Σ+g(0) emission band. Estimates of the total electron excitation rates for the nominal b′1Σ+u(1) and c′41Σ+u(0) levels are determined from the spectrum by extrapolating the model through regions containing unmeasured and/or resonantly absorbed band

Vibronic coupling in the superoxide anion: The vibrational dependence of the photoelectron angular distribution

We present a comprehensive photoelectron imaging study of the O₂(X³Σg⁻,v′=0–6)←O₂⁻(X²Πg,v′′=0) and O₂(a¹Δg,v′=0–4)←O₂⁻(X²Πg,v′′=0)photodetachment bands at wavelengths between 900 and 455 nm, examining the effect of vibronic coupling on the photoelectron angular distribution (PAD). This work extends the v′=1–4 data for detachment into the ground electronic state, presented in a recent communication [R. Mabbs, F. Mbaiwa, J. Wei, M. Van Duzor, S. T. Gibson, S. J. Cavanagh, and B. R. Lewis, Phys. Rev. A82, 011401–R (2010)]. Measured vibronic intensities are compared to Franck–Condon predictions and used as supporting evidence of vibronic coupling. The results are analyzed within the context of the one-electron, zero core contribution (ZCC) model [R. M. Stehman and S. B. Woo, Phys. Rev. A23, 2866 (1981)]. For both bands, the photoelectron anisotropy parameter variation with electron kinetic energy,β(E), displays the characteristics of photodetachment from a d-like orbital, consistent with the π∗g 2p highest occupied molecular orbital of O₂⁻. However, differences exist between the β(E) trends for detachment into different vibrational levels of the X³Σg⁻ and a ¹Δg electronic states of O₂. The ZCC model invokes vibrational channel specific “detachment orbitals” and attributes this behavior to coupling of the electronic and nuclear motion in the parent anion. The spatial extent of the model detachment orbital is dependent on the final state of O₂: the higher the neutral vibrational excitation, the larger the electron binding energy. Although vibronic coupling is ignored in most theoretical treatments of PADs in the direct photodetachment of molecular anions, the present findings clearly show that it can be important. These results represent a benchmark data set for a relatively simple system, upon which to base rigorous tests of more sophisticated models.The authors gratefully acknowledge support by the National Science Foundation Grant No. CHE-0748738 and ANU ARC Discovery Projects under Grant Nos. DP0666267 and DP0880850

Source of Nitrogen Isotope Anomaly in HCN in the Atmosphere of Titan

The ^(14)N/^(15)N ratio for N_2 in the atmosphere of Titan was recently measured to be a factor of 2 higher than the corresponding ratio for HCN. Using a one-dimensional photochemical model with transport, we incorporate new isotopic photoabsorption and photodissociation cross sections of N_2, computed quantum-mechanically, and show that the difference in the ratio of ^(14)N/^(15)N between N_2 and HCN can be explained primarily by the photolytic fractionation of ^(14)N^(14)N and ^(14)N ^(15)N. The [HC^(14)N]/[HC^(15)N] ratio produced by N_2 photolysis alone is 23. This value, together with the observed ratio, constrains the flux of atomic nitrogen input from the top of the atmosphere to be in the range (1-2) × 10^9 atoms cm^(-2) s^(-1)

Photodissociation of interstellar N 2

Context. Molecular nitrogen is one of the key species in the chemistry of interstellar clouds and protoplanetary disks, but its photodissociation under interstellar conditions has never been properly studied. The partitioning of nitrogen between N and N

Non-Lorentzian line shapes for interfering rotational resonances in the predissociation of O(2)

Rotationally resolved measurements are presented of interacting predissociating resonances in the Schumann-Runge bands of O₂that exhibit destructive quantum interference for energies between the line centers. The interacting resonances are described using a coupled line shape derived by treating simultaneously the perturbation and predissociation processes using the method of Fano.B. R. Lewis, P. M. Dooley, J. P. England, S. T. Gibson, and K. G. H. Baldwin, L. W. Toro

Vibronic coupling in the superoxide anion: the vibrational dependence of the photoelectron angular distribution

We present a comprehensive photoelectron imaging study of the O2(X 3Σg−,v′ = 0–6)←O2−(X 2Πg,v″ = 0) and O2(a 1Δg,v′ = 0–4)←O2−(X 2Πg,v″ = 0) photodetachment bands at wavelengths between 900 and 455 nm, examining the effect of vibronic coupling on the photoelectron angular distribution (PAD). This work extends the v′ = 1–4 data for detachment into the ground electronic state, presented in a recent communication. Measured vibronic intensities are compared to Franck–Condon predictions and used as supporting evidence of vibronic coupling. The results are analyzed within the context of the one-electron, zero core contribution (ZCC) model. For both bands, the photoelectron anisotropy parameter variation with electron kinetic energy, β(E), displays the characteristics of photodetachment from a d-like orbital, consistent with the πg∗ 2p highest occupied molecular orbital of O2−. However, differences exist between the β(E) trends for detachment into different vibrational levels of the X 3Σg− and a 1Δg electronic states of O2. The ZCC model invokes vibrational channel specific “detachment orbitals” and attributes this behavior to coupling of the electronic and nuclear motion in the parent anion. The spatial extent of the model detachment orbital is dependent on the final state of O2: the higher the neutral vibrational excitation, the larger the electron binding energy. Although vibronic coupling is ignored in most theoretical treatments of PADs in the direct photodetachment of molecular anions, the present findings clearly show that it can be important. These results represent a benchmark data set for a relatively simple system, upon which to base rigorous tests of more sophisticated models

Food Insecurity Prevalence Across Diverse Sites During COVID-19: A Year of Comprehensive Data

Key Findings NFACT includes 18 study sites in 15 states as well as a national poll, collectively representing a sample size of more than 26,000 people. Some sites have implemented multiple survey rounds, here we report results from 22 separate surveys conducted during the year since the COVID-19 pandemic began in March 2020. 18 out of 19 surveys in 14 sites with data for before and since the pandemic began found an increase in food insecurity since the start of the COVID-19 pandemic as compared to before the pandemic. In nearly all surveys (18/19) that measured food insecurity both before and during the pandemic, more Black, Indigenous, and People of Color (BIPOC) were classified as food insecure during the pandemic as compared to before it began. Prevalence of food insecurity for BIPOC respondents was higher than the overall population in the majority of surveys (19/20) sampling a general population. In almost all surveys (21/22), the prevalence of food insecurity for households with children was higher than the overall prevalence of food insecurity. Food insecurity prevalence was higher for households experiencing a negative job impact during the pandemic (i.e. job loss, furlough, reduction in hours) in nearly all surveys and study sites (21/22). Food insecurity prevalence in most sites was significantly higher before COVID-19 than estimates from that time period. Reporting a percent change between pre and during COVID-19 prevalence may provide additional information about the rate of change in food insecurity since the start of the pandemic, which absolute prevalence of food insecurity may not capture. Results highlight consistent trends in food insecurity outcomes since the start of the COVID-19 pandemic, across diverse study sites, methodological approaches, and time