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Rotational Spectroscopic and Computational Studies on Inter/Intramolecular Bonding

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Rotational Spectroscopic and Computational Studies on Inter/Intramolecular Bonding Rotational Spectroscopic and Computational Studies on Inter/Intramolecular Bonding A Thesis Submitted for the Degree of Doctor of Philosophy in the Faculty of Science by Sharon Priya Gnanasekar Department of Inorganic and Physical Chemistry INDIAN INSTITUTE OF SCIENCE Bangalore-560012, India September, 2020 DECLARATION I hereby declare that the work presented in this thesis titled Rotational Spectroscopic and Computational Studies on Inter/Intramolecular Bonding has been carried out by me at the Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore, India, under the supervision of Prof. E. Arunan. September, 2020. Sharon Priya Gnanasekar CERTIFICATE I hereby certify that the work presented in this thesis titled Rotational Spectroscopic and Computational Studies on Inter/Intramolecular Bonding has been carried out by Sharon Priya Gnanasekar at the Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore, India, under my supervision. September, 2020. Prof. E. Arunan Soli Deo gloria ACKNOWLEDGEMENTS This Thesis would not have been possible without the help of many people and I am extremely obliged for all their assistance. I apologize if I have missed any names. I take this opportunity to express my heartfelt gratitude to Prof. Arunan. I am thankful to him for allowing me to work in his lab. I am extremely fortunate to have been allowed to do whatever I wanted. Sir has always encouraged me to pursue whatever I wanted to do. He has been extremely supportive and especially when the spectrometer had stopped working for nearly a year, he was always there in the lab with us trying to make things work. He has always been available, even at odd hours to answer my doubts. He has patiently answered the same questions over and over again till I have understood them. I am grateful to him for teaching me, for being there for me, and for his constant guidance, support and encouragement. As an Int. PhD student I was required to take many courses and I express my gratitude to all my course instructors for teaching with such sincerity and helping me understand the difficult parts of a subject. I would like to specially thank Prof. Vempati and Prof. Vasu for having to teach someone who was unfamiliar with the field. I thank Prof. Sebastian for the opportunity to be a TA for his course. I learnt a lot from him. I appreciate the assistance provided by Prof. Sai Ramesh regarding all things computational. He was always available to help, even with the smallest of problems, for which I am grateful. I would also like to thank Dr. Jayashree Nagesh for her help with understanding the NBO calculations. I am thankful to Prof. Mathias for his help fixing and repairing the various components of the spectrometer. I would also like to thank Dr. Mausumi Goswami for her help with understanding the programs that control the spectrometer. The assistance of Prof. Robert Georges and Prof. Therese Huet in making the visit to Lille possible is acknowledged. I am extremely grateful to Dr. Manuel Goubet for making the experiments with CH3F possible, for his guidance with the experiments and his generous hospitality during my stay in Lille. I am thankful to Dr. Sabath Bteich for her assistance and friendship during my visit to Lille. I would like to acknowledge the fruitful discussions with Dr. Jon Hougen regarding the CH3CN-CO2 spectra. The internal rotor program given to us by Prof. Vadim Ilyushin is deeply appreciated. I would also like to thank Prof. Balaram for giving us a large bottle of acetonitrile. I am grateful to Lakshay Kathuria and Nidhi Sharma for distilling the propargyl alcohol. I acknowledge the help provided by Mr. Lokenathan and Mr. Arul Nambi regarding all electrical and plumbing requirements. The help provided by the cleaning staff in maintaining our lab is deeply appreciated. I would like to thank the past and present Chairmen of IPC and the office staff for all their help with the administrative and official matters. I acknowledge IISc and CSIR for the scholarship. I am thankful to CEFIPRA for the funding to carry out experiments in Lille. I am also thankful to ODAA for the funding to present my work at ISMS-Illinois. I would like to thank Mrs. Arunan for her kindness and generosity. She has always welcomed us to her home for dinners during festivals. She has always extended her assistance whenever I have required it, and I am extremely grateful for the same. I acknowledge my lab mates Dr. Devendra Mani, Dr. Abhishek Shahi, Dr. Sharath, Dr. Emmanuel Etim, Kunal, Kiran, Kabir, Govinda, Arijit, Subharaj, Surabhi, Dipak, Sumaiya, Dr. Sarvesh Pandey for all their help and support. I am also thankful to all the project and UG students who visited our lab. I would like to specially thank Devendra bhaiya and Abhishek bhaiya for patiently answering all my questions, and for teaching me about the spectrometer and the experiment. I am grateful for their constant help and guidance. I would like to thank all the members of the Chemical Dynamics Group meeting. I have learnt a lot from them. I would like to thank Prof. Sebastian, Prof. P. K. Das, Prof. Arunan, Prof. Harbola, Prof. Sai Ramesh and Prof. Bhattacharya for enthusiastically asking questions and explaining concepts. I would like to specially thank Dr. Deepika Janakiraman and Dr. Pallavi Bhattacharya for helping me understand the difficult topics being discussed so that I would be able to follow the presentations. I would like to acknowledge the friendship, encouragement and help extended towards me by my Int. Phd. Batchmates, Aishani, Balaka, Kritika, Nidhi, Veena, Debanjan, Jyotirmoy, Rajesh, Ramkrishna, Rudra, Rupak, Sabyasachi, and Sourav. I would like to thank Sourav for teaching us how to program in LabView. I am especially thankful for the friendship and company of Rudra, Rupak, Balaka, Nidhi and Jyotirmoy. I would also like to thank Kamini di for her friendship. I am thankful to everyone who adopted me to eat with them, so that I never had to eat alone. I am especially thankful to Deep and Arijit for their friendship and all the funny stories. I am grateful to the IISc Basketball Team, for being a place where I could unwind and relax. I am especially thankful to our coach, Digvijay Sir, for taking so much trouble to make sure we were ready for the tournaments. I am thankful to Jaya and Warsha for their friendship. I am extremely grateful to Chirasmita for her love and friendship and for all her help. For being available at odd hours to help me, for encouraging me and supporting me, for their love and friendship, I am forever grateful to my friends Srija and Subhasish, though we are miles apart. For teaching me with enthusiasm and for encouraging my interest in science and maths and for being there for me, I thank my school teachers, Mrs. S. Das, Mrs. B. Elias and Mrs. M. Subramaniam. I express my sincere gratitude to Dr. I Chakraborty and Dr. R. Sharma for making me fall in love with physical chemistry and for their advice, support and constant encouragement. For being my home away from home, I am extremely thankful for Debarati di and Dev bhaiya. I thank them for their advice and encouragement throughout my PhD and am indebted for their help with all my presentations and writing and for proofreading this Thesis. I am deeply grateful to Debarati di for her kindness and affection. I acknowledge her help, support and friendship. I am extremely grateful to Dev bhaiya for his patience and friendship. For being my pillars of support and for their constant prayers and encouragement, I thank my grandparents and parents. I am thankful to them for letting me do whatever I wanted to do and for tolerating the tantrums. I am especially thankful to my mother for proofreading this Thesis despite having no knowledge of Chemistry and for remembering all the molecules I worked with and listening to all the problems with the spectra. I am forever thankful to my sister, for her love and friendship, and for being the cheerleader and critic for everything I do. Lastly, whatever I am able to do, would not be possible without the Almighty. I acknowledge his guiding presence in my life. SYNOPSIS The importance of non-covalent interactions cannot be undermined, as it permeates nearly every sphere of chemistry. The hydrogen bond is the most well-known and ubiquitous non-covalent interaction. In recent times similar interactions involving other elements, that include nearly half the periodic table, have been proposed and studied. The tetrel bond (Group 14 elements) is one such interaction which is analogous to the hydrogen bond1,2. The ‘carbon bond’ is an important subset of these interactions1. Our objective is to understand these non-covalent interactions by studying the structures of weakly bound complexes. Rotational spectroscopy is an extremely accurate technique to obtain the geometrical parameters of molecules in the gas phase. We have used a home-built pulsed nozzle Fourier transform microwave (PNFTMW) spectrometer to record the spectra3. Weakly bound complexes are formed via a supersonic expansion of the gases into a vacuum chamber. These complexes interact with the microwave radiation to give a rotational spectrum. Structural information is then extracted from the rotational spectrum. The rotational spectroscopic studies are supplemented by computational studies such as the Atoms in Molecules theory. There is a paucity of experimental data involving tetrel bonded interactions. This Thesis focusses on hydrogen and tetrel bonded complexes. Chapter 1 of this thesis gives a brief introduction to non-covalent interactions and expounds on the hydrogen and tetrel bonding interactions.
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