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GAS-PHASE ION CHEMISTRY of Mg+', (C - C5H5)Mg"And (C - C5H&Mg+': THEORETICAL and EXPE-NTAL STUDIES

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GAS-PHASE ION CHEMISTRY of Mg+', (C - C5H5)Mg GAS-PHASE ION CHEMISTRY OF Mg+', (C - C5H5)Mg"and (C - C5H&Mg+': THEORETICAL AND EXPE-NTAL STUDIES REBECCA K. MILBURN A thesis submitted to the Faculty of Graduate Smdies in the partial fulfillment of the requirement for the degree of Doctor of Philosophy Graduate Programme in Chernistry York University Toronto, Ontario, Canada October 1999 National Library Bibliothèque nationale du Canada Acquisitions and Acquisitions et Bibjiographic Services services bibliographiques 395 Wellington Street 395. rue Wellington Ottawa ON K1A ON4 Ottawa ON KI A ON4 Canada Canada Your fi& Votre rdfërence Our- Notre rdfBrenca The author has granted a non- L'auteur a accordé une licence non exclusive licence allowing the exclusive permettant à la National Lïbrary of Canada to Bibliothèque nationale du Canada de reproduce, loan, distribute or sell reproduire, prêter, distribuer ou copies of this thesis in microform, vendre des copies de cette thèse sous paper or electronic formats. la forme de microfiche/nlm, de reproduction sur papier ou sur format électronique. The author retains ownership of the L'auteur conserve la propriété du copyright in this thesis. Neither the droit d'auteur qui protège cette thèse. thesis nor substantial extracts £tom it Ni la thèse ni des extraits substantiels may be printed or otherwise de celle-ci ne doivent être imprimés reproduced without the author's ou autrement reproduits sans son permission. autorisation. + + Gas-Phase Ion Chemistry of Mg , (C-C~H~)M~and (c-C H M~+: and Experimental 55L) , Theo~etical Seudies by Rebecca Katherine Milburn a dissertation submitted to the Faculty of Graduate Studies of York University in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY 0 1999 Permission hzs been granted to the LIBRARY OF YORK UNIVERSITY to lend or seIl copies of this dissertation, to the NATIONAL LIBRARY OF CANADA to microfilm this dissertation and to lend or seIl copies of the film, and to UNIVERSITY MICROFILMS to publish an abstract of this dissertation. The author reserves other publication rights, and neither the dissertation nor extensive extracts from it may be printed or otherwise reproduced without the author's written permission. The gas-phase CO-ordination of Mg*, (c-C5H5)MgC and (c-C~H~)~M~in their electronic ground States with a variety of inorganic molecules, cyanides, and sanuated and unsaturated hydrocarbons has been investigated using experimentai and theoretical techniques. Reaction rate coefficients and product distributions were measured with the Selected-Ion Flow ~ub&ollision Induced Dissociation (SIFï/CID) technique operating at (294 c.3) K and a helium buffer gas pressure of (0.35 I0.01) Torr. The results of rnulti-CID studies give insight into bond comectivities and suengths. Molecular orbital caiculations have been performed on a variety of magnesium-contauiuig neutrals and cations in order to determine smictural and themochemical information. For my dad, 1 love you. 1 have a lot of people to thank that have helped me achieve this goal. Most importantly are my mom and dad. Thanks mom and dad! 1would like to express my appreciation to Professor AC. Hopkuison for his patience and support without which 1might not have even started graduate school. 1 would also like to sincerely thank Professor D.K. Bohme for aLl the vatuable guida&e and for allowing me to expand my education in an experimentai settbg. 1have also been fortunate to be helped by a lot of great people; Professor LM. Goodings, Dr. C.F. Rodriquez, Dr. V.I. Baranov, Dr. Y. Ling, Dr. A-E. Ketviais, Dr. J. Sun, Aiwin Cunje, Steve Qum, Tamer Shoeib, Greg Ko yanagi, Doina Caraiman, Diana Sargla, Rob, Claire and Avi. LIST OF PUBLICATIONS Gas-Phase Co-ordination of Mgt, (c-CsH5)Mg' and (c-c5H&~gCwith Saturated Hydrocarbons- Milburn, R.K.; Hopkinson, AC; Bohme, D-K. J. Phys. Chern. A (submitted)- A Smdy of complexes of Mg(NH3)." and Ag(NH3),,', where n = 1-8: Cornpetition Between Direct Coordination and Solvation Through Hydrogen Bonding. Shoeib, T-; Milbuni, R.K.; Koyanagi, G.I.; Lavrov, V.V.; Bohme, D.K.; Siu, K.W.M.; Hopkinson, A.C. (in press). Themochemical Properties of Molecules and ~ahonsof MgN,H, (n=1,2 and m=l- 6): Enthaplies of Formation, Proton Minicies and Ionization Energies. Miiburn, R.K.; Hopkinson, AC.; Bohme, D.K. (in preparation). Sm&-ring Carbenes Carrying a Positive Charge: the Effects of Substituting by CN in c-Ca3+. Milburn, R.K; Hopkinson, A.C.; Bohme, D.K. Int. Mass Specrrom. (in press). Dimer Cations of Cyanoacetylene: Theoretical Isomers and Their Laboratory Production in the Absence and Presence of cao2f Implications for InterstellarICircumstek Chemistry. Milburn, R.K.; Sun, I.; Baranov, V.I.; Hopkinson, A.C.; Bohme, D.K. Phys. Chem. A 1999,103,7528. Gas-Phase Co-ordination of Mg, (c-C5H5)Mg+ and (C-C~H~)~M~+with Srnail Inorganic Ligands. Milbum, R.K; Baranov, V.I.; Hopkinson, A.C.; Bohme, D.K. J. Phys. Chern, A 1999,103,6373. Experimentai and Theoretical Studies of the Basicity and Proton-Affinity of Si& and the Structure of SiFX. Ling, Y.; Milburn, R.K; Hopkinson, AC.; Bohme, D.K. J. Am. Soc. Mass Spectrom. 1999, 10, 848. Magnesium Chemistry in the Gas Phase: Calculated Thennodynamics Properties and Experimental Ion Chemistry in Hz-Oz-Nt Flames. Chen, Q.F.; Milbum, R.IC ; Hopkinson, AC.; Bohme, DK; Goodings, J.M. Int. J. Mass Spectrom. Ion Processes 1999,184,153. Sequential Ligation of Mgf, Fe+, (c-C5Hs)Mg', and (c-c5H5)Fe+with Ammonia in the Gas Phase: Transition from Coordination to Solvation in the Sequential Ligation of Mgt. Milburn, RK; Baranov, V.I.; Hopkinson, AC.; Bohme, D.K. J. Phys. Chern. A 1998,102,9803. vii Destabilised Carbocations: A Cornparison of the CtH&SC and c2H4NOf Potential Energy Surfaces. Rodrïquez, CF.; Vuckovic, D.Lj.; Milburn, R.K-; Hopkinson, A.C. J. Mol. Struct., Theochem, 1997,401,117. Theoretical Enthalpies of Formation of N'&Cl,: Neutra1 Molecules, Cations and Anions. Milbum, RK;Rodrïquez, CF.; Hopkinson, A.C. Phys. Chern. B 1997, 101, 1837. TABLE OF CONTl3NTS Page Abstract iv Acknowledgements vi List of Publications vii List of Tables xiv List of IUustrations xvi METHODS OF INVESTIGATION 2.1. Experimental Methods 2.1.1. IonSource 2.1.2. Quadmpole Mass Analzyer 19 2.1.3. Venturi Gas Aspirator 2.1 -4. Gas Inlet S ystem 2.1.4.1. Carrier U-aç Flow 2.1 .M. Neutral Reactant Gas 23 2.1.5. Multi-Collision Induced Dissociation 25 2.1.6.1. Reactions with no Si3-cant Reverse or 26 FherReaction 2.1 -6.2. Higher Order Reaction with no 5i-cant Reverse Reaction 2.1.6.3. Reaction with Si,anificant Reverse Reaction 2.1 -7- References 2.2- Theoretical ,Methods 2.2.1 - The Schr6dinger Equation 2.2.2. Hartree-Fock Theory 2.2.3. MQller-Plesset Theory 40 2.2.4. Coupled Clusters and Confiovation Interaction 41 Theory 3-25 Density Functionai Theory 42 2.2.5.2. Becke-3 Lee-Yang-Pan (B3LYP) 45 2.2.6. Basis Sets 46 2.2.7. Thermochemical Corrections 47 2.2.8. References 49 3. INORGANIC MOLECULES (H7, m, H20, &, CO, NO, 02¶COt, NO, NO3 3.1 - Introduction 50 3 2. Results and Discussion 55 Reactions with MgC 55 Reactions with (c-~sHs)Mg+ 62 Reactions with (c-CsHs)lMg" 80 Variation in the Rate of Ligation with the Number 83 of (c-CsH5)Ligands 3.2.5, Variation in the Rate of Ligation with the Nwnber 84 of Ligands, L 3.2.6. Structure and Bonding 87 3 -3. Conclusions 91 3 -4. References 4. SATURATED, UNSATURATED AND CYCLIC ENDROCARBONS 4.1. Introduction 96 4.2. Results and Discussion 98 4.2.1. Saturated Hydrocarbons 4.2.2. Unsaturated Hydrocarbons 4.2.3. Cyclic Hydrocarbons 4.3. Structure and Bonding 124 4.4. Variation in the Rate of Ligation with the Number of Ligands 126 4.5. Conclusions 128 4.6. References S. CYANIDE AND ISOCYANIDE MOLECLXES 5.1. Introduction 5 2. Results and Discussion 5.2.1. Reactions with HCN 5.2.2. Reactions with CH3CN and CHaC 5.2.3. Reactions with H2C=CHCN 5.2.4. Reactions with HC* xi 5.3. Strucnue and Bonding of Mg+/HC3N 147 5.4, Possible Mechanism for the Formation of Cyclooctatetraene 162 5.5. Conclusions 166 5 -6. References 169 THERMOCHEMICAL PROPERTIES OF MgN& AND MgOnH, 6.1. Introduction 170 6.2. Results and Discussion 17 1 6.2.1. Structural Details 17 1 6.2.2. Themochemical Properties 6.2.2.1. Enthdpies of Formation 6.2.2.2. Proton Affinities 6.2-2-3. Ionization Energies 6.2.2-4. Binding Energes 6.3. Conclusions 190 6.4. References 19 1 DIMER CATIONS OF CYANOACTYLENE: A THEORETICAL STUDY 7.1. Introduction 192 7.2. Results and Discussion 193 7.2.1. Review of Previous Experimental Results 193 7.2-2. Theoretical Results 197 7.3. Conchsions 212 7.4. References 217 8. FUTURE WORK 8.1. Future Work 8.2. References 9. APPENDIX 9.1. List of Illustrations and Tables LIST OF TABLES Table Page 3.1. Measured rate coefficients for the reactions of ground states of Mg*, (c-CsHs)Mg+ and (c-C5H5)?Mf with selected inorganic ligands. 3.2. Room temperame equilibrium constants for ligation reactions with selected inorganic ligands. 3.3. Computed total elecnonic energies at B 3LYW6-3 l+G(d), vibrational zero-point energies and thermal energies of Mg(N&)n*, where n = 1-6. 3 -4. Cdculated binding enthalpies at 298 K at B3LYP/6-3 1+G(d) of Mg(NH3)n*, where n = 1-6.
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