Photodissociation and reaction dynamics of chlorine-containing species important in stratospheric ozone chemistry

Chlorine oxide species have received considerable attention in recent years due to their central role in the balance of stratospheric ozone. Many questions pertaining to the behavior of such species still remain unanswered and plague the ability of researchers to develop accurate chemical models of the stratosphere. Presented in this thesis are three experiments that study various properties of some specific chlorine oxide species.

In the first chapter, the reaction between ClONO_2 and protonated water clusters is investigated to elucidate a possible reaction mechanism for the heterogeneous reaction of chlorine nitrate on ice. The ionic products were various forms of protonated nitric acid, NO_2 +(H_20)_m, m = 0, 1, 2. These products are analogous to products previously reported in the literature for the neutral reaction occurring on ice surfaces. Our results support the hypothesis that the heterogeneous reaction is acid-catalyzed.

In the second chapter, the photochemistry of ClONO_2 was investigated at two wavelengths, 193 and 248 nm, using the technique of photofragmentation translational spectroscopy. At both wavelengths, the predominant dissociation pathways were Cl + NO_3 and ClO + NO_2. Channel assignments were confirmed by momentum matching the counterfragments from each channel. A one-dimensional stratospheric model using the new 248 nm branching ratio determined how our results would affect the predicted Cl_x and NO_x partitioning in the stratosphere.

Chapter three explores the photodissociation dynamics of Cl_2O at 193, 248 and 308 nm. At 193 nm, we found evidence for the concerted reaction channel, Cl_2 + O. The ClO + Cl channel was also accessed, however, the majority of the ClO fragments were formed with sufficient internal energies for spontaneous secondary dissociation to occur. At 248 and 308 nm, we only observed only the ClO + Cl channel. . Some of the ClO formed at 248 nm was formed internally hot and spontaneously dissociated. Bimodal translational energy distributions of the ClO and Cl products indicate two pathways leading to the same product exist.

Appendix A, B and C discuss the details of data analysis techniques used in Chapters 1 and 2. The development of a molecular beam source of ClO dimer is presented in Appendix D.

Extractive institutions in colonial Africa

A common explanation for African current underdevelopment is the extractive character of institutions established during the colonial period. Yet, since colonial extraction is hard to quantify and its exact mechanisms are not well understood, we still do not know precisely how colonial institutions affect economic growth today. In this project, I study this issue by focusing on the peculiar structure of trade and labor policies employed by the French colonizers.

First, I analyze how trade monopsonies and coercive labor institutions reduced African gains from trade during the colonial period. By using new data on prices to agricultural producers and labor institutions in French Africa, I show that (1) the monopsonistic character of colonial trade implied a reduction in prices to producers far below world market prices; (2) coercive labor institutions allowed the colonizers to reduce prices even further; (3) as a consequence, colonial extraction cut African gains from trade by over 60%.

Given the importance of labor institutions, I then focus on their origin by analyzing the colonial governments' incentives to choose between coerced and free labor. I argue that the choice of institutions was affected more by the properties of exported commodities, such as prices and economies of scale, than by the characteristics of colonies, such indigenous population density and ease of settlement for the colonizers.

Finally, I study the long-term effects of colonial trade monopsonies and coercive labor institutions. By combining archival data on prices in the French colonies with maps of crop suitability, I show that the extent to which prices to agricultural producers were reduced with respect to world market prices is strongly negatively correlated with current regional development, as proxied by luminosity data from satellite images. The evidence suggests that colonial extraction affected subsequent growth by reducing development in rural areas in favor of a urban elite. The differential impact in rural and urban areas can be the reason why trade monopsonies and extractive institutions persisted long after independence.

Cavity-enhanced spectroscopies for applications of remote sensing, chemical kinetics and detection of radical species

This thesis describes applications of cavity enhanced spectroscopy towards applications of remote sensing, chemical kinetics and detection of transient radical molecular species. Both direct absorption spectroscopy and cavity ring-down spectroscopy are used in this work. Frequency-stabilized cavity ring-down spectroscopy (FS-CRDS) was utilized for measurements of spectral lineshapes of O₂ and CO₂ for obtaining laboratory reference data in support of NASA’s OCO-2 mission. FS-CRDS is highly sensitive (> 10 km absorption path length) and precise (> 10000:1 SNR), making it ideal to study subtle non-Voigt lineshape effects. In addition, these advantages of FS-CRDS were further extended for measuring kinetic isotope effects: A dual-wavelength variation of FS-CRDS was used for measuring precise D/H and ¹³C/¹²C methane isotope ratios (sigma>0.026%) for the purpose of measuring the temperature dependent kinetic isotope effects of methane oxidation with O(¹D) and OH radicals. Finally, direct absorption spectroscopic detection of the trans-DOCO radical via a frequency combs spectrometer was conducted in collaboration with professor Jun Ye at JILA/University of Colorado.