In the interstellar medium, cosmic rays comprised mostly of high-energy protons can drive fast non-thermal reactions in the ice mantles covering microscopic dust grains. Illustrated here is such a collision, highlighting the tracks (shown in red) of both the cosmic ray and "secondary electrons" that are formed in the ice. This track was generated using the CIRIS program (Shingledecker et al., 2017). ON COSMIC RAYS IN ASTROCHEMICAL MODELS Christopher Nelson Shingledecker Virginia Beach, Virginia B.Sc. Chemistry with Highest Distinction University of Virginia, 2013 A Dissertation Presented to the Graduate Faculty of the University of Virginia in Candidacy for the Degree of Doctor of Philosophy Department of Chemistry University of Virginia April 2018 ii ⃝c Copyright by Christopher Nelson Shingledecker All rights reserved May 12, 2018 iii ABSTRACT OSMIC rays are known to have significant physicochemical impact on interstellar regions (Indriolo and McCall, 2013). For example, even in the very first astro- chemical modeling work of Herbst and Klemperer (1973), cosmic rays were shown to drive the gas-phase chemistry of molecular clouds through the ion- + Cization of H2 and subsequent formation of H3 . Later, Prasad and Tarafdar (1983) demon- strated that cosmic rays - and the secondary electrons they generate - could collisionally excite the Lyman and Werner bands of H2, leading to the formation of internal UV pho- tons in dense regions where the external interstellar UV radiation field is quickly attenu- ated. However, despite the central role that the ionization and excitation of H2 currently plays in astrochemical models, extending the treatment of these types of interactions to other species has proven challenging thanks to both the complexity and variety of under- lying microscopic processes, which has stymied the development of suitable theoretical and computational techniques. In spite of these difficulties, radiation chemistry remains astrochemically attractive since, as demonstrated by an extensive body of work in labora- tory astrophysics, non-thermal reactions triggered ice irradiation can lead to the formation of even complex organic molecules (Holtom et al., 2005; Hudson and Moore, 2001; Hudson et al., 2008; Rothard et al., 2017). Therefore, we have developed new techniques for mod- eling solid-phase cosmic ray-induced radiation chemistry in both detailed microscopic Monte Carlo models and more general models utilizing rate equations. Where possible, re- sults from our new models are compared with previous experimental data and found to be in good agreement. Finally, we have incorporated solid-phase radiation chemistry into an existing chemical network in order to examine the impact of such reactions on the abun- dances of species in cold cores. Our results suggest that cosmic ray-driven chemistry is indeed a powerful formation mechanism which both increases the abundance of complex organic molecules and improves the agreement between models and observations. Thus, given the ubiquity of cosmic rays in the interstellar medium and their substantial physic- ochemical impact, as shown in part by the new computational results presented here, we conclude that, similar to photochemistry, radiation chemistry - particularly in interstellar ices - should become a standard component of future astrochemical models. iv To Anna ICO igitur, quod necessarium est, quod orbis totius natura aut sim- plex est, nihil in se habens nisi homogenia quæ unius formæ et unius dispositionis et virtutis sunt, sicut quælibet pars ignis est ig- nis, aut est naturæ compositæ habens in se diversa secundum for- Dmam et dispositionem. Nos autem videmus oculis nostris, quod orbis non est naturæ unius et unius formæ et dispositionis: quoniam sunt in ipso et sphæræ diversæ et partes diversæ: quarum una non est stellata, et altera non suscipit lumen non habens: et talis diversitas formarum et dispositionum non est in eo quod naturæ simplicis et homogenium... - Sanctus Albertus Magnus De causis proprietatum elementorum Lib.II, tract.1, cap.1 De elementis cælum componentibus v Committee Members: Eric Herbst Brooks H. Pate Sergei A. Egorov Robin T. Garrod Robert E. Johnson vi PREFACE & ACKNOWLEDGEMENTS N the Spring of 2014, about half way through my second year of graduate school, I had yet to really settle on a major project for my dissertation. It was around that time that my research advisor, Eric Herbst, attended the 168th Faraday Discussion on the “Astrochemistry of Dust, Ice, and Gas.” Upon returning to Charlottesville, he Isuggested that I might “study how high-energy protons and electrons interact with grains and what reactions they can cause.” The chief inspiration for this endeavor was, I think, the paper presented by Mason et al. (2014) on the astrochemical promise of secondary electrons, which are formed in material exposed to ionizing radiation. In that work, Mason and coworkers remarked that “the astrochemistry community can and should assimilate data from [the experimental radiation chemistry] community relevant to their research.” In the context of astrochemistry, radiation chemistry is extremely attractive, since a large body of experimental work has shown it to be a means by which even complex molecules can be formed at low temperatures. My initial “exposure” to the field of radiation chemistry came in the form of an over- stuffed folder containing about a dozen or so papers - including Mason et al. (2014). Care- fully going through the contents of that folder - and other works I discovered along the way - constituted how I spent the bulk of my time during the summer of 2014. My ini- tial, and naïve, idea was that it should be possible merely to pluck a ready made radiation chemistry model off the shelf, so to speak, which I could then use to study the bombard- ment of interstellar ices by cosmic rays. Very quickly however, I realized that, on the one hand, there were very nice radiation track models, and on the other, that there were very nice chemical models, but that there was no single program which satisfactorily com- bined the two. By the Fall of 2014, after my intensive summer crash course, I became con- vinced that it was possible to write such a combined model, i.e. one that could calculate both radiation tracks and the chemical evolution of an irradiated solid. About three years and ∼5,000 lines of Fortran code later, I published Shingledecker et al. (2017), which pre- sented CIRIS, the Chemistry of Ionizing Radiation in Solids program. My work develop- ing this detailed Monte Carlo model as well as collaborations with experimenters further convinced me that a simplified macroscopic generalization of the microscopic events sim- ulated in CIRIS was urgently needed to spur the incorporation of cosmic ray-driven grain chemistry into astrochemical networks. Fortuitously, our group had recently received an vii invitation to submit a paper to a special issue of Physical Chemistry Chemical Physics, which was to be focused on “theory, experiment, and simulations in laboratory astrochemistry.” That invitation proved to be the necessary motivation to develop the general theoretical framework described in Shingledecker and Herbst (2018). Finally, in Shingledecker et al. (2018), we made our first attempt to shed light on whether radiation chemistry could drive the formation of large astronomical molecules and found that the bombardment of dust particles by cosmic rays could indeed enhance the abundances of such species. Reaching this point would have been impossible without the patience, guidance, in- struction, and assistance of a veritable cloud of individuals. First and foremost, I wish to express my sincerest gratitude to Eric Herbst. Over my time working with him, first as an undergraduate and later as a graduate student, he has been an invaluable mentor and an amazing research supervisor. His clarity and incisiveness in teaching is the gold standard to which I aspire, and he is also my model for professional collegiality and scientific good taste. In addition, I wish to thank Karin Öberg, another valued mentor and colleague who, along with Eric, introduced me to astrochemistry and helped considerably with my first first-author paper. I’ve also learned much from the many post-docs who have been with the group during my time at UVa, viz. Anton Vasyunin, Qiang Chang, Tatiana Vasyunina, Ugo Hincelin, Kinsuk Acharyya, and Romane Le Gal - all of whom have my profound thanks for putting up with innumerable naïve questions. During my time in graduate school, I’ve had the privilege of working with many fan- tastic people. First, I wish to thank two of my fellow UVa class of 2013 grads, Ryan Loomis and Jennifer Bergner (Wahoowa!), whom I have had the honor of knowing since the very beginning of my adventures in astrochemistry. Special thanks also to Anthony “Tony” Remijan and the merry band of rabble rousers that comprise the “Kingdom of Remi- janistan,” in particular Brett McGuire and Andrew Burkhardt. From Tony, I’ve learned the value of forthrightness in communication, leadership skills, and even some sage re- lationship advice. He also taught me that, as a modeler, I should have some skin in the game - that I need to go out on a limb and make predictions that observers can test. Brett McGuire - big molecule hunter extrordinaire - has a boundless energy, relentless drive, and infectious enthusiasm that makes science really exciting. Brett is also the most naturally gifted public speaker I know, and his presentations have been, for me, master classes in scientific communication. Finally, Andrew and I started graduate school together and his friendship has made the journey a real joy. Over the last five years, I’ve come to appreciate his personal qualities - empathy, levelheadedness, and a sense of humor - as much as his work ethic, creativity, and resourcefulness. In addition to the help I’ve received from research advisors, group members, and col- leagues, I could not have reached this point without the instruction and guidance of my teachers and professors - especially Sergei Egorov, James Demas, Ian Harrison, and Kevin Lehmann.