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OBSERVATION OF THE INFRARED SPECTRUM OF THE HELIUM-HYDRIDE MOLECULAR ION Item Type text; Dissertation-Reproduction (electronic) Authors Tolliver, David Edward Publisher The University of Arizona. Rights Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author. Download date 07/10/2021 23:40:49 Link to Item http://hdl.handle.net/10150/282038 INFORMATION TO USERS This was produced from a copy of a document sent to us for microfilming. While the most advanced technological means to photograph and reproduce this document have been used, the quality is heavily dependent upon the quality of the material submitted. The following explanation of techniques is provided to help you understand markings or notations which may appear on this reproduction. 1.The sign or "target" for pages apparently lacking from the document photographed is "Missing Page(s)". If it was possible to obtain the missing page(s) or section, they are spliced into the film along with adjacent pages. This may have necessitated cutting through an image and duplicating adjacent pages to assure you of complete continuity. 2. When an image on the film is obliterated with a round black mark it is an indication that the film inspector noticed either blurred copy because of movement during exposure, or duplicate copy. Unless we meant to delete copyrighted materials that should not have been filmed, you will find a good image of the page in the adjacent frame. 3. When a map, drawing or chart, etc., is part of the material b^ing photo­ graphed the photographer has followed a definite method in "sectioning" the material. It is customary to begin filming at the upper left hand corner of a large sheet and to continue from left to right in equal sections with small overlaps. If necessary, sectioning is continued again—beginning below the first row and continuing on until complete. 4. For any illustrations that cannot be reproduced satisfactorily by xerography, photographic prints can be purchased at additional cost and tipped into your xerographic copy. Requests can be made to our Dissertations Customer Services Department. 5. Some pages in any document may have indistinct print. In all cases we have filmed the best available copy. University Microfilms International 300 N. ZEEB ROAD, ANN ARBOR, Ml 48106 18 BEDFORD ROW, LONDON WC1R AEJ, ENGLAND 8017776 TOLLIVER, DAVID EDWARD OBSERVATION OF THE INFRARED SPECTRUM OF THE HELIUM- HYDRIDE MOLECULAR ION The University of Arizona PH.D. 1980 University Microfilms International 300 N. Zeeb Road, Ann Arbor, MI 48106 18 Bedford Row, London WCIR 4EJ, England OBSERVATION OF THE INFRARED SPECTRUM OF THE HELIUM HYDRIDE MOLECULAR ION by David Edward Tolliver A Dissertation Submitted to the COMMITTEE ON OPTICAL SCIENCES (GRADUATE) In Partial Fulfillment of the Requirements For the Degree of DOCTOR OF PHILOSOPHY In the Graduate College THE UNIVERSITY OF ARIZONA 198 0 THE UNIVERSITY OF ARIZONA GRADUATE COLLEGE As members of the Final Examination Committee, we certify that we have read the dissertation prepared by David Edward Tolliver entitled Observation of the Infrared Spectrum of the Helium Hydride Molecular Ion and recommend that it be accepted as fulfilling the dissertation requirement for the Degree of Doctor of Philosophy / j n •; •-> —1 j .1 O / ^ 17 Date7" /O f &(. j A'r o /2. i /'fi d JDate - g/^L/l,\A "f . ^ ^ 61 Date ^-C. V V?.l/ 8 b Date Date Final approval and acceptance of this dissertation is contingent upon the candidate's submission of the final copy of the dissertation to the Graduate College. I hereby certify that I have read this dissertation prepared under my direction and recommend that it be accepted as fulfilling the dissertation requirement. If- 1^ Dissertation Director Date STATEMENT BY AUTHOR This dissertation has been submitted in partial fulfillment of requirements for an advanced degree at The University of Arizona and is deposited in the University Library to be made available to borrow­ ers under rules of the Library. Brief quotations from this dissertation are allowable without special permission, provided that accurate acknowledgment of source is made. Requests for permission for extended quotation from or reproduc­ tion of this manuscript in whole or in part may be granted by the head of the major department or the Dean of the Graduate College when in his judgment the proposed use of the material is in the interests of schol­ arship. In all other instances, however, permission must be obtained from the author. SIGNEDDoa^J F- AU that U> gold doeA not glitten, Not all thoie who wande.fi one loit; The old that. ih A&iong doeA not wltkeA, Veep nootA a/ie not reached by the fanott. Fn.om the aAhes a fa-Oie ihall be woken, A tight (JKom the t>hadow& ihaLt Ap>u.ng; Renewed t>hall be blade that u)a& broken: The cAownlea again bhaJUL be king. iii ACKNOWLEDGMENTS I would like to acknowledge the guidance of my research director, Dr. William H. Wing, and my academic advisor, Dr. Richard L. Shoemaker, during the course of my graduate study at the Optical Sciences Center. I would like to thank Professor Willis E. Lamb, Jr. for helpful and stimulating discussions regarding this research and physics in general. I am grateful to Dr. Joseph J. Spezeski for encouragement, valuable discussions, and a careful reading of the manuscript. I also acknowledge the collaboration on this research of Dr. George A. Kyrala. The contri­ butions of Mr. David R. Wickholm and Mr. August H. Johnson toward the development and construction of the apparatus is appreciated. The excel­ lent typing and editorial skills of Ms. Elaine Segura is much appreciated. This research was supported in part by the National Science Foundation; the National Bureau of Standards Precision Measurement Grant Program; the U.S. Air Force Office of Scientific Research and the U.S. Army Research Office; the Petroleum Research Fund, administered by the American Chemical Society; and the University of Arizona Physics Department. Lastly, I would like to thank my wife for many years' patience in somewhat trying circumstances. iv TABLE OF CONTENTS Page LIST OF ILLUSTRATIONS vii LIST OF TABLES ix ABSTRACT x 1. INTRODUCTION 1 Interest in Molecular Ions 1 History of and Current Interest in HeH 5 Summary of Chapters 8 2. SUMMARY OF THE THEORY OF THE STRUCTURE OF HeH+ 9 Electronic States in HeH+ 9 Vibrational-Rotational States 15 Hyperfine Structure 24 Application to HeH+ 25 Peripheral Theoretical Treatments of HeH 27 3. REVIEW OF PREVIOUS EXPERIMENTAL WORK ON HeH+ 28 Experiments on Molecular Bond Strength . 29 Unimolecular and Collision-Induced Dissociation of HeH . 30 Dissociation of Fast HeH Ions Traversing Thin+Foils . 31 Observation of the Infrared Radiation from HeH 32 4. EXPERIMENTAL METHOD 35 The Doppler Tuned Ion Beam Laser Resonance Method ... 36 Ion Source Population Distribution 38 Doppler Tuning 40 Laser-Molecule Interaction 43 Collisional Detection Mechanism 47 Signal-to-Noise Ratio Estimate 52 5. APPARATUS 56 Experiment Framework 56 Ion Beam Vacuum System 59 Ion Source 63 Production Mechanisms of HeH+ 63 Ion Source Design 70 Ion Source Performance 78 v vi TABLE OF CONTENTS--Continued Page Ion Beam Optics 80 Carbon Monoxide Laser 90 Optical Cavity and Mechanical Design 90 Laser Power Supply 92 Laser Cooling and Gas Filling Systems 102 Laser Frequency Control 106 Passive Stabilization 106 Active Stabilization 106 Frequency Calibration 112 Laser Beam Optics 114 Signal Processing, Data Acquisition, and Computer Control 119 Signal Processing 120 Microcomputer System Hardware . 121 Microcomputer Software 124 Computer Programs 127 6. EXPERIMENTAL RESULTS AND DISCUSSION 129 Experimental Procedure 129 Method of Data Analysis 132 Analysis of Experimental Linewidths and Uncertainties . 136 Linewidth Contributions 136 Frequency Measurement Uncertainties 139 Presentation of Results and Comparison with Present Theory 141 Comment on the Implications of the Present Work 143 Comment on Possible Future Work 144 APPENDIX A: COMPREHENSIVE LISTINGS OF THEORETICAL WORK ON HeH+ 145 APPENDIX B: VIBRATIONAL-ROTATIONAL SELECTION RULES AND APPROXIMATE TRANSITION DIPOLE MOMENT CALCULATION 152 APPENDIX C: LISTING OF THE MICROCOMPUTER EXPERIMENT CONTROL PROGRAM 158 LIST OF REFERENCES 167 LIST OF ILLUSTRATIONS Figure Page 1. Correlation diagram for HeH+ 13 2. Potential energy curves for some low lying states of HeH+ 16 3. Electron density contours for ground state HeH+ 17 4. (^He^H)+ infrared emission spectrum obtained by Raitz Von Frentz et al 34 5. Doppler tuned ion beam laser resonance method concepts . 37 6. Doppler tuned ion beam laser resonance method schematic . 39 7. Optical table-ion beam framework 58 8. High vacuum system schematic 60 9. Ion-molecule reaction kinetics diagram 66 10. Theoretical population distribution for HeH+ 68 11. Ion source schematic 71 12. Ion source wiring diagram 74 13. Focusing electrode power supply schematic 76 14. Ion source flange 77 15. Ion source performance 79 16. Ion beam optics schematic 83 17. Ion beam electrical wiring schematic 84 18. Gas target detail 86 19. Beam defining aperture detail 88 20. Laser current regulator circuit schematic 94 21. Laser current controller circuit schematic 96 vii viii LIST OF ILLUSTRATIONS--Continued Figure Page 22. Laser current controller logic circuit schematic 98 23. PZT/bushing current sensors schematic 99 24. Laser anode current sensors schematic 100 25. Laser gas fill system schematic 105 26. Laser stabilization scheme 108 27. Laser frequency locking loop schematic 110 28. PIT driver/amplifier circuit schematic 113 29. Integrating digital voltmeter schematic 122 30. Stepping motor driver/interface circuit schematic .... 125 31. Chart recorder trace of the (1,ll)«-»-(0,12) resonance .

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