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Ann Arbor, Ml 48106 The vn Band of Cyanuric Fluoride and The A ‘II - X 1S + Transition of Aluminum Monobromide A Dissertation Presented in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy in the Graduate School of the Ohio State University By Patrick E. Fleming * * * * * The Ohio State University 1994 Approved By: Dissertation Committee: Prof. James V. Coe Prof. Roger E. Gerkin Prof. C. Weldon Mathews Advisor Department of Chemistry To my students, past and future. ii Acknowledgements I wish to express my most sincere gratitude to my preceptor, Professor C. Weldon Mathews for his continual guidance during the completion of the projects presented in this document. I also wish to thank Professors James Coe, Roger Gerkin, Harry McSwiney and Russell Pitzer for critical readings of this document and portions thereof and also for many helpful suggestions and discussions concerning the content of this document. I would like to thank the many former and current members of the research group including Drs. Barbara Sweeting and Michael Armijo. Also, gratitude is due to Kelly Mahoney and Richard Brett for a great deal of help and advise in recent years. Further, my survival over the past several years has been greatly aided by the friendship of several colleagues including Kenneth Cowen, Christopher Carter and Timothy Wright who will always be remembered for saving the new Chemistry Building from the "Great flood of 1994" and several amusing games of Hacky-Sack. Also, I would like to thank my good friends Cynthia Capp, Deborah McCarthy, Otto Fruedenberg, John Szpylka, Jed Mellott and Frank Seeley. Their contributions to the quality of my life will not be forgotten. I must also express my gratitude to all of the fine people at Ohio Wesleyan University who aided me in affording me my first solo opportunity at teaching on the college level. Lastly, I would like to thank all of the current and past members of the Campus Dart League and the Wednesday night dart league at Ledos. To all, throw well! Vita January 16, 1963 Born - Torrance, California 1985 B.S. in Chemistry University of Notre Dame Du Lac Notre Dame, Indiana 1988 M.S in Physical Chemistry The Ohio State University Columbus, Ohio 1985 - 1992 Graduate Teaching Associate Department of Chemistry The Ohio State University Columbus, Ohio 1992 - 1994 Assistant Professor of Chemistry, Department of Chemistry Ohio Wesleyan University Delaware, Ohio Field of Study Major Field: Chemistry Studies in Molecular Spectroscopy Professor C. Weldon Mathews iv Table of Contents D edication ...............................................................................................................................................ii Acknowledgements ......................................................................................................................... iii V ita ...................................................................................................................................................... iv Table of Contents ................................................................................................................................ v List of Tables ................................................................................................................................ viii List of Figures ................................................................................................................................... ix CHAPTER I - Introduction ............................................................................................................ I A. Principles of Fourier Transform Spectroscopy ............................................... 1 B. Light Collection Optics for the Bruker IFS 120 HR Spectrometer .............................................................................................................3 i. Principles of Design ....................................................................................3 ii. Implementation ...........................................................................................4 C. Least-Squares fitting of Spectral Data ............................................................ 6 R eferences ........................................................................................................................... 18 CHAPTER II - The v„ Band of Cyanuric Fluoride ............................................................... 19 A. Historical Background ........................................................................................ 19 B. Experimental C o n siderations...............................................................................21 CHAPTER II (Continued) C. Spectral Interpretation and Analysis ....................................................................25 i. Vibrational Interpretation .........................................................................25 ii. Rotational Analysis .....................................................................................26 D. Discussion and Conclusions ..................................................................................30 i. Structural Considerations .........................................................................32 R eferences .............................................................................................................................. 35 CHAPTER III - Aluminum Monobromide ................................................................................ 36 A. Introduction ...............................................................................................................36 B. Experimental Details ..............................................................................................38 C. Isotopomer Identification .......................................................................................39 D. Rotational Analysis .................................................................................................44 E. Conclusions ...............................................................................................................50 R eferences .............................................................................................................................. 51 CHAPTER IV - Other Experiments............................................................................................ 53 A. The Electronic Spectrum of FCN ........................................................................53 i. Production of FCN ....................................................................................55 ii. Observations in the Laboratory ............................................................56 B. Steady State Observation of Radicals Containing C N .....................................58 R eferences .............................................................................................................................. 60 CHAPTER V - Conclusions ...........................................................................................................63 Bibliography ........................................................................................................................................64 vi Appendix A - Assignments for the v„ and vn + v14-vI4 Bands of Cyanuric Fluoride ................................................................................................. 67 Appendix B - Assignments for the A - X Transition of Aluminum Monobromide ......................................................................................74 Appendix C - VIB-DIST.BAS .........................................................................................................97 Appendix D - ABC.BAS and related program s .................................................................... 113 Appendix E - CHEW.BAS and