John D. Baldeschwieler

Ion cyclotron resonance spectroscopy

Ion cyclotron resonance spectroscopy yields information on many aspects of ion-molecule chemistry. The method is ideally suited for experiments involving ion energies below several electron volts, and hence provides a valuable complement to other techniques (27). eyclotron double resonance is uniquely suitable for establishing relationships between reactant ions and their product ions in complex ion-molecule reaction sequences. The double-resonance experiments with isotopic species yield information on reaction mechanisms and the nature of intermediate species. Ion-molecule reactions which occur at low energies are quite sensitive to the nature of functional groups and the details of molecular structure (28). Reactions of ions or neutral molecules with specific reagents in the cyclotron spectrometer can thus be used to characterize unknown species. Once the systematic ion-molecule chemistry of useful reagents has been worked out, it should be possible to proceed in a manner directly analogous to classical chemical methods. Suppose, for example, that reagents A+, B+, C+, and D+ each have characteristic reactions with different functional groups. Then these reagents can all be mixed with an unknown neutral species, X, and each of the reactions, X + A+ → ?, X + B+ → ?, . . . . can be examined. In contrast to solution chemistry, all the reagents can be added simultaneously to the unknown, since each of the specific reactions can be examined by cyclotron double resonance. The reactions which occur, the species synthesized , and the products of degradation then characterize X. The same methodology can be applied to characterize an unknown ionic epecies X+, through use of neutral reagents A, B, C, and D. For example, proton transfer reactions to neuteal species have been applied in studying ions of mass 45 produced from various sources (29). The order of the proton affinities of the neutral reagent molecules are as follows: NH3 〉 isobutylene 〉 propene. Ions of mass 45 can be produced by the protonation of ethylene oxide (see structure III), the protonation of acetaldehyde (see structure IV), and the fragmentation of dimethyl ether (see structure V). Those ions might be expected to have, respectively, the three structures: Proton transfer from the mass-45 ions from sources III and IV to NH3 and to isobutylene occurs readily, but not proton transfer to propene. For the ion from source V, proton transfer to NH3 occurs, but not proton transfer to isobutylene or propene. Thus the proton transfer reactions to various neutral reagents demonstrate that the mass-45 ions from the various sources are different. This example is only a rudimentary version of an approach to the characterization of unusual ionic species; niore sophisticated applications can follow when the systematic chemistry of more reagents is available. This approach should be ideal for comparing nonclassical carbonium ions produced by different routes. Some very interesting ionic species are produced by rearrangements in the fragmentation of molecules, following electron impact. Such molecular rearrangements frequently result in the fragmentation of an ion radical to another ion radical with the elimination of a small neutral species (30). It should be possible to run these reactions in reverse to check the postulated mechanisms. An interesting result of the systematic study of proton transfer to various functional groups is the finding that the proton affinity of various amines and pyridine is extremely high (31). Species such as VI and VII: might be expected to be very stable; they are in fact so stable that they are unreactive with respect to subsequent chemistry at the charge center. Thus, if there are other functional groups on the ion, the important reactions should occur at these functional groups. It should be possible to design species for which the presence of the charge has little influence on the reactivity of a neutral functional group. In this case the charge functions simply as an inert label which makes the study of neutral-neutral reactions accessible by cyclotron resonance: Various routes for development of the basic technique also appear to be very promising. Echo phenomena following sequences of pulsed excitation have been observed in electron cyclotron resonance (32). Analogous transient phenomena should also occur in ion cvclotron resonances (33). Pulsed-cyclotron-resonance techniques of course have intriguing analogies to nuclear-magnetic-resonance spin-echo experiments (34) and may be the technique of choice for making accurate measurements of ion-molecule-reaction cross sections as a function of energy for low ion energies. Finally, many ion-molecule reactions yield products in excited electronic states (35). For example, the reaction N2- + CO → N2 + CO- (46) has been studied by beam techniques (36). A straightforward procedure is to observe optical emission from the cyclotron spectrometer by placing a window at the end of the cyclotron cell (37). The emission can be analyzed with a crude set of optical filters, or with a high-speed spectrograph. Optical emission from the cyclotron cell can of course originate from many sources. The radiation from a specific excited product ion can be selected by a radio-frequency-optical double-resonance experiment. If, in the generai reaction A+ + B → *C+ + D, (47) ion A+ is irradiated at its cyclotron resonance frequency, the number density of optical emitters *C+ is changed. If the irradiating frequency is modulated, then the number of optical emitters will be modulated, so that the intensity of emission from *C+ will also be modulated. When the optical emission from *C+ is analyzed in a spectrograph with a photoelectric cell, the output of the photoelectric cell can be detected with a phase sensitive detector referenced to the modulation frequency. This highly specific modulation-detection scheme should discriminate against other sources of light in the cyclotron cell.

Ion‐Cyclotron Double Resonance

A charged particle in a uniform moving magnetic field H describes a circular orbit in a plance perpendicular to H with an angular frequency or cyclotron frequency omagae. When an alternating electric field E(t) is applied normal to H at omegae, the ions absorb energy from the alternating electric field, and are accelerated to larger velocities and orbital radii. [1] The absorption of energy from E(t) at the cyclotron resonance frequency can be conveniently detected using a marginal oscillator detector. When the ions accelerated by E(t) collide with other particles, they lose some of their excess energy. A mixture of ions and neutral molecules in the presence of H and E(t) then reaches a steady-state condition in which the energy gained by the ions from E(t) between collisions is lost to the neutral molecules in collisions.

Diffusion of Water in Zeolites

The self-diffusion coefficient D of water occluded in samples of near-faujasite has been determined by pulsed field-gradient spin-echo nuclear magnetic resonance. The value of D in square centimeters per second x 105 at 30�C is 1.34, 1.65, and 1.88 in the following zeolites, respectively: Na X, Ca X, and Ca Y (X and Y being an indication of ratio of silicon to aluminum in the zeolites). By comparison, the value of D in pure water at 30�C is 2.5 x 10-5 cm2/sec. Arrhenius activation energies for D are 6.9, 6.8, and 5.6 kilocalories per mole, respectively, for the three faujasites and 5.0 kcal/mole for pure water. Thus, there appears to be little difference in diffusion behavior between free water and water occluded in faujasite.

Fourier transform C-13 nmr analysis of some free and potassium-ion complexed antibiotics.

Abstract Fourier transforms of the noise-decoupled, natural abundance 13C nmr free induction decays of the cyclic antibiotic valinomycin and its potassium-ion complex have been obtained at 25.2 MHz. Comparisons are made with 13C nmr spectra taken at 22.6 MHz of the cyclic antibiotic nonactin and the synthetic polyether dicyclohexyl-18-crown-6 and their potassium complexes. The resonances of the carbonyls directly coordinating the potassium ion in valinomycin and nonactin shift downfield about 4 ppm upon complex formation. Smaller but comparable shifts in both up- and downfield directions for carbons away from the binding site are observed by comparisons of the spectra of free and complexed nonactin and the polyether. This suggests that conformational rearrangements of the molecule as a whole can compete with direct interactions between carbons and the potassium ion in determining 13C chemical shift differences between the free and complexed species.