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Urszula Szczepaniak Spectroscopy and Photochemistry of Astrophysically-Relevant Molecules of the Cyanoacetylene Family

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Urszula Szczepaniak Spectroscopy and Photochemistry of Astrophysically-Relevant Molecules of the Cyanoacetylene Family NNT: 2017SACLXXXX Urszula Szczepaniak PhD Thesis Spectroscopy and photochemistry of astrophysically-relevant molecules of the cyanoacetylene family Supervisor: Prof. dr hab. Robert Kołos Co-Supervisor: Dr hab. Claudine Crépin-Gilbert, Directrice de Recherches au CNRS This work was prepared in the frame of joint Polish-French programme cotutelle: at International Doctoral Studies at the Institute of Physical Chemistry, Polish Academy of Sciences, ul. Kasprzaka 44/52, 01-224 Warsaw, POLAND and at Université Paris Saclay, Université Paris Sud - Paris XI, ÉCOLE DOCTORALE No 572: Ondes et Matière, DISCIPLINE: Physique; Institut des Sciences Moléculaires d'Orsay, Bat. 210, Domaine de l'Université de Paris Sud, 91400 Orsay FRANCE. Doctoral committee: Prof. dr hab. Jerzy Herbich Institute of Physical Chemistry, PAS President Prof. dr hab. Robert Kołos Institute of Physical Chemistry, PAS Supervisor Dr hab. Claudine Crépin-Gilbert Institut des Sciences Moléculaires d'Orsay Co-Supervisor Prof. dr hab. Maciej Nowak Institute of Physics, PAS Reviewer Dr hab. Maria Wierzejewska University of Wrocław Reviewer Dr hab. Séverine Boyé-Péronne Université de Paris Sud Examiner Prof. dr hab. Joanna Sadlej Warsaw University Examiner Public defence planned for June 2017, at the Institute of Physical Chemistry, Polish Academy of Sciences. Warsaw, March 2017 Rodzicom ACKNOWLEDGMENTS ACKNOWLEDGMENTS I would like to express my gratitude to my supervisors Prof. Robert Kołos and Prof. Claudine Crépin-Gilbert who trusted that even without proper background knowledge I would be able to work in the field of spectroscopy and matrix isolation, for the guidance, support, and all the lessons I learnt (and those that I refused to learn), for being helpful and friendly (not only when it comes to science, but also in other areas of life), and for many hours spent on helping me present the obtained results in a better way (until the very end of the writing process). A group of people invested their time in reading the manuscript and helping me improve it, to whom I am thankful: my Supervisors, Tom, Marcin, Natalia, Asia, Michèle, and Krzysiek. Thank you for all the contributions to removing the mistakes, suggested additions and refinements of the text that improved it immeasurably. I cannot imagine this work to be completed without help of a whole group of scientists to whom I owe a debt of gratitude. I would like to thank Jean-Claude Guillemin for the syntheses of chemical compounds that I used, Marcin Gronowski – for the quantum computations without which I could not support the presented identifications and for the help with the computations I did, Michał Turowski – for the guidance in the lab work, help in analyses, and the theoretical predictions that backed my first experiments with long chains formation, Thomas Custer – for help both in the lab and with analyses, the data for preparing graphs and for corrections of both language and content of this Thesis. I would also like to thank all colleagues from ISMO (Equipe D) for being very welcoming, patient, and helpful, especially: Michèle Chevalier and Alejandro Gutiérrez-Quintanilla, with whom I worked directly, and Catherine Le Bris and Thierry Chamaillé for the help with lasers. I would also like to thank people whose presence in my life encouraged me to pursue scientific path in the direction of physical chemistry, starting from Christian Jungnickel and Wojciech Chrzanowski who have successfully encouraged me to continue my education after undergraduate studies. I owe a debt of gratitude to Gyorgyi Remenyi and Mark E. Casida, who offered me patience and kindness and who also took the effort of putting something into my head. Gentlemen, one of you taught me about cryogenics, the other about spectroscopy. Look what that led to! I learnt a lot from Stéphane Douin who introduced me to the technique of CRDS (that unfortunately didn't find its place in this thesis). Thank you for that. I am also thankful to Tomonari Wakabayashi, for the discussions at conferences and after them, for letting me use the original data from his article in this Thesis, as well as for the quizzes and insight to Japanese culture. I am deeply indebted to all the people from administration division, both in IPC PAS and in ISMO, especially Danuta Dudek, Joanna Wiszniowska, Joanna Pińkowska, Jadwiga Skrzecz, Magdalena Szustak, Martine Basset, Marie-Claire Paul, Bernadette Rome, Audrey Colin and Annie Le Gal. Thanks to you my studies and travels between laboratories were as smooth as they could be. v Spectroscopy and photochemistry of astrophysically relevant molecules of the cyanoacetylene family There is a big group of people that I am thankful to for their support, encouragement and good words in times of frustration, but also for the distraction that they were able to provide letting me get some rest and perspective when it was needed. Thank you for your patience in this intense time. That is mainly addressed to my parents, who always granted me support and guidance from the very beginning of my life, and who taught me things that made me want explore the world. I am also thankful to my friends, Mariola, Michał Ś., Artur, Ali, Michał Ż., Karolina, Gosia, and Rafał for being there for me, and to all the wonderful people that I was lucky to meet during my PhD studies. Natalia, Krzysztof R. K., Krzysztof S., Tom, Ania, Lek, Valerii, Ephriem, Ivan A., Feriel, Felipe, Cristiano, Gabriela, Ariel, Ivan C., Rolando, Thejus, Gerard, Nina, Martin, Mathieu, Themis, Odélie, people from CCOF, and many more: thank you all for the discussions, whether they were on spectroscopy, general science or topography and metro system of Paris, Madrid or Havana. Thank you for letting me learn a new perspective, for sharing nice moments, introducing me to didgeridoo, trips we made, coffee we drank, movies we watched (or made), things we explored, and songs we sang, for being helpful and welcoming. Even though I was away from home, thanks to you it felt like home, anyway. Thank you for that. Finally, I am also thankful to brothers Y. for helping me reduce the pressure to the right amount, as well as to all the (unnamed here) superheroes and gods that helped me survive every day. This work was financially supported by: the French Government scholarship Bourse Eiffel, managed by Campus France; Polish National Science Centre, project No. 2011/03/B/ST4/02763; PICS (Programmes Internationaux de la Coopération Scientifique): PAN-CNRS (2014-2016); French–Polish Partenariat Hubert-Curien Polonium project (2012-2013 and 2015- 2016) of scientific cooperation; the project “Scholarships for PhD students of Podlaskie Voivodeship”; the project was co-financed by the European Social Fund, Polish Government and Podlaskie Voivodeship*; Polish National Science Centre, project No. 2015/17/B/ST4/03875. *Autorka pracy doktorskiej była uczestniczką projektu „Stypendia dla doktorantów województwa podlaskiego” współfinansowanego ze środków Europejskiego Funduszu Społecznego, środków budżetu państwa oraz ze środków budżetu Województwa Podlaskiego. Projekt był realizowany na podstawie Umowy o dofinansowanie projektu Instytucji Pośredniczącej w ramach Programu Operacyjnego Kapitał ludzki 2007 – 2013, nr POKL.08.02.02-20-002/12. Działanie 8.2.Transfer wiedzy, Poddziałanie 8.2.2. Regionalne Strategie Innowacji. vi TABLE OF CONTENTS TABLE OF CONTENTS GLOSSARY ........................................................................................................................... ix ABSTRACT ........................................................................................................................... xi 1 INTRODUCTION ........................................................................................................... 1 1.1 Astrophysically-relevant molecules and processes ................................................... 1 1.2 Cyanoacetylene family – cyano(poly)ynes spectroscopy and cryogenic synthesis of carbon-nitrogen chains ........................................................................................................ 7 1.3 The goal: spectroscopy of available and newly-created molecules ........................ 11 2 MATERIALS, TECHNIQUES AND METHODS ....................................................... 15 2.1 Providing stability: cryogenic matrix isolation ....................................................... 15 2.2 Spectroscopy ........................................................................................................... 17 2.2.1 Vibrational spectroscopy ................................................................................. 17 2.2.2 Electronic spectroscopy ................................................................................... 19 2.3 Chemicals ................................................................................................................ 20 2.4 Sample preparation ................................................................................................. 22 2.5 Cryostat ................................................................................................................... 23 2.6 Gas-phase experiments ........................................................................................... 24 2.7 Photochemical experiments .................................................................................... 24 2.8 Spectroscopic measurements .................................................................................. 25 2.8.1 Infrared absorption spectroscopy measurements
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