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Photographs included in the original manuscript have been reproduced xerographically in this copy. Higher quality 6" x 9" black and white photographic prints are available for any photographs or illustrations appearing in this copy for an additional charge. Contact UMI directly to order. BeH & Howell Information and Learning 300 North Zeeb Road, Ann Arbor, MI 48106-1346 USA Dynamics of Harpooning Studied by Transition State Spectroscopy Andrew J. Hudson A thesis submitted in conformity with the requirements for the degree of Doctor of Philosophy. Graduate Department of Chemistry, in the University of Toronto. O Copyright by Andrew J. Hudson National Library Bibliotheque nationale I*I of Canada du Canada Acquisitions and Acquisitions et Bibliographic Services services bibliogmphiques 395 Wellington Street 395, rue Wellington Ottawa ON K 1A ON4 Ottawa ON KIA ON4 Canada Canada Your tm Vorre mlsrsnce Our fi& Notre relereme The author has granted a non- L'auteur a accorde une licence non exclusive licence allowing the exclusive pennettant a la National Library of Canada to Bibliotheque nationale du Canada de reproduce, loan, distribute or sell reproduire, prster, distribuer ou copies of this thesis in microform, vendre des copies de cette these sous paper or electronic formats. la forme de rnicrofiche/film, de reproduction sur papier ou sur format electronique. The author retains ownership of the L'auteur conserve la propriete du copyright in this thesis. Neither the droit d'auteur qui protege cette these. thesis nor substantial extracts fkom it Ni la these ni des extraits substantiels may be printed or othewise de celle-ci ne doivent 6tre imprimes reproduced without the author's ou autrement reproduits sans son permission. autorisation. Thesis Abstract Dynamics of Harpooning Studied by Transition State Spectroscopy Andrew J. Hudson Department of Chemistry, University of Toronto The van der Waals complexes. Na-XR (X=F.C1. Br, R=CH3; and X=F. R=H),have been generated by crossing a beam of sodium with the expansion region of a supersonic jet of the appropriate halide in an inert-carrier gas. The complexes were identifled by photoionization time-of-flight mass spectrometry. Depletion of the complexes was observed following photoexcitation using a broad range of wavelengths. 711. Initial excitation of the Na chromophore within the complex is believed to be followed by charge-transfer dissociation; An experimental study of the photodepletion of Na-XR complexes has been made, and the results have been compared to recent ab initio studies of the same process. Photoexcitation of Na-XR accesses a potential-energy surface (PES)for the reaction Na*+XR+NaX+R, at a configuration intermediate between the reactants. Na*+XR, and products. NaX+R. We. therefore. den0te the excited-state species as a transition state. TS, indicated by the t symbol. The starting configuration for the TS, [Na*-XFt]*, is determined by the geometry of Na-XR and the excitation energy, hv 1. Consequently, by varying the wavelength, h 1, we are able to access selected TS configurations. This constitutes a Transition State Spectroscopy for these classic 'harpooning' reactions. As the excitation energy is further increased, we are able to access the TS for the reaction of XR with successively higher electronically-excited states of Na*. The dynamics of the excited-state reaction have been probed by measuring the depletion cross-section for the ground-state complex as a fiction of the excitation wavelength. In addition. the lifetime of the TS was estimated by measuring an ion signal for photoionization directly from the TS. The TS is believed to dissociate via surface-hopping from the electronically- excited state into alternate channels on the ground-state PES. The surface hop occurs in the region in which the character of the TS changes from iargely covalent to largely ionic. [~a*4Rl$-t[Na+4CFt-] * : this is the harpooning event proposed over half a century ago to be the crucial step in the reaction of alkali metals with halogens. iii Acknowledgments I sincerely thank John Polanyi for his support during the work described in this thesis. It has been a memorable experience working under his guidance. I am greatly indebted to Jixing Wang and Rudolf Ehlich for teaching me experimental techniques and for their participation in the measurements of the Na-XCH3 (X= F. C1. Br) and Na-FH photodepletion spectra. I would like to thank Han Bin Oh for his participation in the measurement of the Transition State ionization spectrum for [~a*-FH]*. This work was made especially interesting as a result of a successful collaboration with theoreticians from our group. Xiao Yan Chang provided ab initio calculations of the minimum-energy structures. binding energies and vibrational frequencies for Na-XCH3 and Na*-XCH3 complexes. Piotr Piecuch provided detailed ab initio calculations of the complete potential-energy surface for the ground and electronically-excited states of NaFH. An analytical fit to the ab initio potential energies for NaFH calculated in this laboratory was obtained by Don Truhlar and Maria Topaler at the University of Minnesota. From this analytical fit they were able to calculate the vibrational-energy levels and Franck-Condon factors for vertical transitions and, thereby, simulate a photoabsorption spectnun for Na- FH. Their results contributed to a greater understanding of the experimental spectra. I would like to thank Jamie Donaldson for many helpful discussions and in particular for leading us to identifylng a Transition State Metime for [Na*-FHI* from measurements of the depletion intensity as a function of the excitation-laser fluence. Also, thanks to Giacinto Scoles for noticing that the Na beam was a supersonic expansion and correcting our value for the collision energy of the molecular beams. Finally, I would like to acknowledge British Gas for a Research Scholarship and the University of Toronto for an International Student Award. The experiments were financed by the National Science and Research Council (NSERC)and Photonics Research Ontario (PRO). Table of Contents Chapter 1 Introduction 1.1 Photofnduced reaction in weakly bound systems 1.2 'Ikansition State Spectroscopy 1.8 Harpooning reactions Reaction of Na atoms with methyl halide molecu tes Reaction of Na atoms with Mi' molecules 1.4 Summary and thesis preview Chapter 2 Experiment 2.1 Experimental apparatus Vacuum system Crossed-molecular beam ussembf y Excitation loser, L1 Ionization laser, Timesf-flight mass spectrometer Timing circuitry 2.2 Data Analysis Mossspectm Photodepletion meastlrements 2.3 Summarp Chapter 3 Photodepletion of Na-XCa3: X=F. C1. Br 3.1 Identification of complexes 3.2 Structure of complexes 3.3 Photodepletion measurements 3.4 Discussion peak dgnment peak intensity vibrational structure 3.5 Summary Chapter 4 Photodepletion of Na-FH 4.1 Identification of Na-FH complexes 4.2 Photodepletion measurements 4.3 Discussion Oylomics of the photoinduced reaction Vibrational stmcture ond intensity of the photodepletion peaks Chapter 6 Transition State ionization of Na-FCH3 5.1 Experiment 5.2 Results 5.3 Discdon 5.4 su.nmary Chapter 6 Conclusions and future directions 6.1 Conclusion 6.2 Future directions Thesis Summary References vii List of f&wes Figure 1;1: The covalent. M+X2, and ionic. M++&-. interaction potentials lor the alkali metal and halogen molecule. Figure 2.1: Side view of the vacuum system. Figure 2.2: Crossed-molecular beam assembly. Figure 2.3: TOF mass spectrum obtained by expansion of a mixture of CH30H and Hz0 in Ar-carrier gas through the pulsed valve. Figure 2.4: Top view of the reaction chamber indicating the path of the excitation laser, L1,and the ionization laser. La. Figure 2.5: TOF mass spectrum obtained by expansion of a 2.5% mixture of HF in He at 250kPa backing pressure through the pulsed valve. Figure 2.6: Power dependence of the ionization signal for Na-FH measured at 248nm. Ffeure 2.7: Power dependence of the depletion signal for Na-FH measured at hl= 660 nm. Figure 2.8: The ion-signal intensity for Na-FH as a function of the time delay between the ionization laser, and the onset of the pulsed-extraction field. Figure 2.9: The ion-signal intensity for NaaeFH as a function of the backing pressure for the pulsed valve and the time delay between the ionization laser, h,and the pulsed valve. viii Figure 2.10: Norma.lised ion-signal intensity for Na-FH as a function 49 of the time delay between the ionization laser. Lz, and the excitation laser. i1. Figure 3.2: TOF ion spectra for Na+XCH3. X=F,Cl,Br,I. 58 Figure 3.2: Power dependence of the ion signals for Na. NaI and 62 Na2I in the TOF spectra. Geometry and dissociation energy of the most stable 66 configurations for Nab-XCH3. X=F.C1, Br. I. Figure 3.4: Action spectra for Na-XCH3.