16 resultados para controlling mass fuzzy

em CaltechTHESIS


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This thesis presents composition measurements for atmospherically relevant inorganic and organic aerosol from laboratory and ambient measurements using the Aerodyne aerosol mass spectrometer. Studies include the oxidation of dodecane in the Caltech environmental chambers, and several aircraft- and ground-based field studies, which include the quantification of wildfire emissions off the coast of California, and Los Angeles urban emissions.

The oxidation of dodecane by OH under low NO conditions and the formation of secondary organic aerosol (SOA) was explored using a gas-phase chemical model, gas-phase CIMS measurements, and high molecular weight ion traces from particle- phase HR-TOF-AMS mass spectra. The combination of these measurements support the hypothesis that particle-phase chemistry leading to peroxyhemiacetal formation is important. Positive matrix factorization (PMF) was applied to the AMS mass spectra which revealed three factors representing a combination of gas-particle partitioning, chemical conversion in the aerosol, and wall deposition.

Airborne measurements of biomass burning emissions from a chaparral fire on the central Californian coast were carried out in November 2009. Physical and chemical changes were reported for smoke ages 0 – 4 h old. CO2 normalized ammonium, nitrate, and sulfate increased, whereas the normalized OA decreased sharply in the first 1.5 - 2 h, and then slowly increased for the remaining 2 h (net decrease in normalized OA). Comparison to wildfire samples from the Yucatan revealed that factors such as relative humidity, incident UV radiation, age of smoke, and concentration of emissions are important for wildfire evolution.

Ground-based aerosol composition is reported for Pasadena, CA during the summer of 2009. The OA component, which dominated the submicron aerosol mass, was deconvolved into hydrocarbon-like organic aerosol (HOA), semi-volatile oxidized organic aerosol (SVOOA), and low-volatility oxidized organic aerosol (LVOOA). The HOA/OA was only 0.08–0.23, indicating that most of Pasadena OA in the summer months is dominated by oxidized OA resulting from transported emissions that have undergone photochemistry and/or moisture-influenced processing, as apposed to only primary organic aerosol emissions. Airborne measurements and model predictions of aerosol composition are reported for the 2010 CalNex field campaign.

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In Part I of this thesis, a new magnetic spectrometer experiment which measured the β spectrum of ^(35)S is described. New limits on heavy neutrino emission in nuclear β decay were set, for a heavy neutrino mass range between 12 and 22 keV. In particular, this measurement rejects the hypothesis that a 17 keV neutrino is emitted, with sin^2 θ = 0.0085, at the 6δ statistical level. In addition, an auxiliary experiment was performed, in which an artificial kink was induced in the β spectrum by means of an absorber foil which masked a fraction of the source area. In this measurement, the sensitivity of the magnetic spectrometer to the spectral features of heavy neutrino emission was demonstrated.

In Part II, a measurement of the neutron spallation yield and multiplicity by the Cosmic-ray Underground Background Experiment is described. The production of fast neutrons by muons was investigated at an underground depth of 20 meters water equivalent, with a 200 liter detector filled with 0.09% Gd-loaded liquid scintillator. We measured a neutron production yield of (3.4 ± 0.7) x 10^(-5) neutrons per muon-g/cm^2, in agreement with other experiments. A single-to-double neutron multiplicity ratio of 4:1 was observed. In addition, stopped π^+ decays to µ^+ and then e^+ were observed as was the associated production of pions and neutrons, by the muon spallation interaction. It was seen that practically all of the π^+ produced by muons were also accompanied by at least one neutron. These measurements serve as the basis for neutron background estimates for the San Onofre neutrino detector.

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This thesis presents structural investigations of molecular ions and ionic clusters using vibrational predissociation spectroscopy. Experimentally, a pulsed beam of the mass-selected ion is crossed by a tunable infrared laser beam generated by a Nd:YAG pumped LiNbO_3 optical parametric oscillator. The resulting fragment ion is mass-analyzed and detected, with its intensity as a function of the laser wavelength being the "action" spectrum of the parent ion. In the case of SiH_7^+, we observed a vibrational band centered at 3866 cm^(-1) with clear P, Q, R branches, which is assigned as a perturbed H_2 stretch. The absence of a second H_2 band suggests that the ion forms a symmetric complex with a structure H_2•SiH_3^+•H_2 , in contrast to the species CH_7^+, which has the structure CH_5^+•H_2. The infrared spectra of NO_2^+(H_2O)_n clusters exhibit a marked change with cluster size, indicating that an intracluster reaction occurs with sufficient solvation. Specifically, in NO_2^+(H_2O)_n clusters where n≤3, H_2O binds to a nitronium ion core; but at n=4 the NO_2^+ reacts, transforming the cluster to a new structure of H_3O^+•(H_2O)_(n_2)•HNO_3. For protonated chlorine nitrate, we have observed two distinct isomers previously predicted by ab initio calculations: NO_2^+•(HOC1), the lowest energy isomer, and (ClO)(HO)NO^+, a covalently bonded isomer about 20 kcal/mol higher in energy. Both isomers decompose to NO_2^+ and HOCl upon photo-excitation. These results for HClONO_2^+ lend strong support to the involvement of an ionic mechanism in the reaction of ClONO_2 on polar stratospheric cloud surfaces, a critical step in the dramatic springtime depletion of ozone over Antarctica. Current research activities on halide-solvent clusters and metal-ligand complexes as well as technological improvements of the apparatus are also discussed.

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We study the fundamental dynamic behavior of a special class of ordered granular systems in order to design new, structured materials with unique physical properties. The dynamic properties of granular systems are dictated by the nonlinear, Hertzian, potential in compression and zero tensile strength resulting from the discrete material structure. Engineering the underlying particle arrangement of granular systems allows for unique dynamic properties, not observed in natural, disordered granular media. While extensive studies on 1D granular crystals have suggested their usefulness for a variety of engineering applications, considerably less attention has been given to higher-dimensional systems. The extension of these studies in higher dimensions could enable the discovery of richer physical phenomena not possible in 1D, such as spatial redirection and anisotropic energy trapping. We present experiments, numerical simulation (based on a discrete particle model), and in some cases theoretical predictions for several engineered granular systems, studying the effects of particle arrangement on the highly nonlinear transient wave propagation to develop means for controlling the wave propagation pathways. The first component of this thesis studies the stress wave propagation resulting from a localized impulsive loading for three different 2D particle lattice structures: square, centered square, and hexagonal granular crystals. By varying the lattice structure, we observe a wide range of properties for the propagating stress waves: quasi-1D solitary wave propagation, fully 2D wave propagation with tunable wave front shapes, and 2D pulsed wave propagation. Additionally the effects of weak disorder, inevitably present in real granular systems, are investigated. The second half of this thesis studies the solitary wave propagation through 2D and 3D ordered networks of granular chains, reducing the effective density compared to granular crystals by selectively placing wave guiding chains to control the acoustic wave transmission. The rapid wave front amplitude decay exhibited by these granular networks makes them highly attractive for impact mitigation applications. The agreement between experiments, numerical simulations, and applicable theoretical predictions validates the wave guiding capabilities of these engineered granular crystals and networks and opens a wide range of possibilities for the realization of increasingly complex granular material design.

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Improved measurement of the neutrino mass via β decay spectroscopy requires the development of new energy measurement techniques and a new β decay source. A promising proposal is to measure the β energy by the frequency of the cyclotron radiation emitted in a magnetic field and to use a high purity atomic tritium source. This thesis examines the feasibility of using a magnetic trap to create and maintain such a source. We demonstrate that the loss rate due to β decay heating is not a limiting factor for the design. We also calculate the loss rate due to evaporative cooling and propose that the tritium can be cooled sufficiently during trap loading as to render this negligible. We further demonstrate a design for the magnetic field which produces a highly uniform field over a large fraction of the trap volume as needed for cyclotron frequency spectroscopy while still providing effective trapping.

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The initial probabilities of activated, dissociative chemisorption of methane and ethane on Pt(110)-(1 x 2) have been measured. The surface temperature was varied from 450 to 900 K with the reactant gas temperature constant at 300 K. Under these conditions, we probe the kinetics of dissociation via trapping-mediated (as opposed to 'direct') mechanism. It was found that the probabilities of dissociation of both methane and ethane were strong functions of the surface temperature with an apparent activation energies of 14.4 kcal/mol for methane and 2.8 kcal/mol for ethane, which implys that the methane and ethane molecules have fully accommodated to the surface temperature. Kinetic isotope effects were observed for both reactions, indicating that the C-H bond cleavage was involved in the rate-limiting step. A mechanistic model based on the trapping-mediated mechanism is used to explain the observed kinetic behavior. The activation energies for C-H bond dissociation of the thermally accommodated methane and ethane on the surface extracted from the model are 18.4 and 10.3 kcal/mol, respectively.

The studies of the catalytic decomposition of formic acid on the Ru(001) surface with thermal desorption mass spectrometry following the adsorption of DCOOH and HCOOH on the surface at 130 and 310 K are described. Formic acid (DCOOH) chemisorbs dissociatively on the surface via both the cleavage of its O-H bond to form a formate and a hydrogen adatom, and the cleavage of its C-O bond to form a carbon monoxide, a deuterium adatom and an hydroxyl (OH). The former is the predominant reaction. The rate of desorption of carbon dioxide is a direct measure of the kinetics of decomposition of the surface formate. It is characterized by a kinetic isotope effect, an increasingly narrow FWHM, and an upward shift in peak temperature with Ɵ_T, the coverage of the dissociatively adsorbed formic acid. The FWHM and the peak temperature change from 18 K and 326 K at Ɵ_T = 0.04 to 8 K and 395 K at Ɵ_T = 0.89. The increase in the apparent activation energy of the C-D bond cleavage is largely a result of self-poisoning by the formate, the presence of which on the surface alters the electronic properties of the surface such that the activation energy of the decomposition of formate is increased. The variation of the activation energy for carbon dioxide formation with Ɵ_T accounts for the observed sharp carbon dioxide peak. The coverage of surface formate can be adjusted over a relatively wide range so that the activation energy for C-D bond cleavage in the case of DCOOH can be adjusted to be below, approximately equal to, or well above the activation energy for the recombinative desorption of the deuterium adatoms. Accordingly, the desorption of deuterium was observed to be governed completely by the desorption kinetics of the deuterium adatoms at low Ɵ_T, jointly by the kinetics of deuterium desorption and C-D bond cleavage at intermediate Ɵ_T, and solely by the kinetics of C-D bond cleavage at high Ɵ_T. The overall branching ratio of the formate to carbon dioxide and carbon monoxide is approximately unity, regardless the initial coverage Ɵ_T, even though the activation energy for the production of carbon dioxide varies with Ɵ_T. The desorption of water, which implies C-O bond cleavage of the formate, appears at approximately the same temperature as that of carbon dioxide. These observations suggest that the cleavage of the C-D bond and that of the C-O bond of two surface formates are coupled, possibly via the formation of a short-lived surface complex that is the precursor to to the decomposition.

The measurement of steady-state rate is demonstrated here to be valuable in determining kinetics associated with short-lived, molecularly adsorbed precursor to further reactions on the surface, by determining the kinetic parameters of the molecular precursor of formaldehyde to its dissociation on the Pt(110)-(1 x 2) surface.

Overlayers of nitrogen adatoms on Ru(001) have been characterized both by thermal desorption mass spectrometry and low-energy electron diffraction, as well as chemically via the postadsorption and desorption of ammonia and carbon monoxide.

The nitrogen-adatom overlayer was prepared by decomposing ammonia thermally on the surface at a pressure of 2.8 x 10^(-6) Torr and a temperature of 480 K. The saturated overlayer prepared under these conditions has associated with it a (√247/10 x √247/10)R22.7° LEED pattern, has two peaks in its thermal desorption spectrum, and has a fractional surface coverage of 0.40. Annealing the overlayer to approximately 535 K results in a rather sharp (√3 x √3)R30° LEED pattern with an associated fractional surface coverage of one-third. Annealing the overlayer further to 620 K results in the disappearance of the low-temperature thermal desorption peak and the appearance of a rather fuzzy p(2x2) LEED pattern with an associated fractional surface coverage of approximately one-fourth. In the low coverage limit, the presence of the (√3 x √3)R30° N overlayer alters the surface in such a way that the binding energy of ammonia is increased by 20% relative to the clean surface, whereas that of carbon monoxide is reduced by 15%.

A general methodology for the indirect relative determination of the absolute fractional surface coverages has been developed and was utilized to determine the saturation fractional coverage of hydrogen on Ru(001). Formaldehyde was employed as a bridge to lead us from the known reference point of the saturation fractional coverage of carbon monoxide to unknown reference point of the fractional coverage of hydrogen on Ru(001), which is then used to determine accurately the saturation fractional coverage of hydrogen. We find that ƟSAT/H = 1.02 (±0.05), i.e., the surface stoichiometry is Ru : H = 1 : 1. The relative nature of the method, which cancels systematic errors, together with the utilization of a glass envelope around the mass spectrometer, which reduces spurious contributions in the thermal desorption spectra, results in high accuracy in the determination of absolute fractional coverages.

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Trace volatile organic compounds emitted by biogenic and anthropogenic sources into the atmosphere can undergo extensive photooxidation to form species with lower volatility. By equilibrium partitioning or reactive uptake, these compounds can nucleate into new aerosol particles or deposit onto already-existing particles to form secondary organic aerosol (SOA). SOA and other atmospheric particulate matter have measurable effects on global climate and public health, making understanding SOA formation a needed field of scientific inquiry. SOA formation can be done in a laboratory setting, using an environmental chamber; under these controlled conditions it is possible to generate SOA from a single parent compound and study the chemical composition of the gas and particle phases. By studying the SOA composition, it is possible to gain understanding of the chemical reactions that occur in the gas phase and particle phase, and identify potential heterogeneous processes that occur at the surface of SOA particles. In this thesis, mass spectrometric methods are used to identify qualitatively and qualitatively the chemical components of SOA derived from the photooxidation of important anthropogenic volatile organic compounds that are associated with gasoline and diesel fuels and industrial activity (C12 alkanes, toluene, and o-, m-, and p-cresols). The conditions under which SOA was generated in each system were varied to explore the effect of NOx and inorganic seed composition on SOA chemical composition. The structure of the parent alkane was varied to investigate the effect on the functionalization and fragmentation of the resulting oxidation products. Relative humidity was varied in the alkane system as well to measure the effect of increased particle-phase water on condensed-phase reactions. In all systems, oligomeric species, resulting potentially from particle-phase and heterogeneous processes, were identified. Imines produced by reactions between (NH4)2SO4 seed and carbonyl compounds were identified in all systems. Multigenerational photochemistry producing low- and extremely low-volatility organic compounds (LVOC and ELVOC) was reflected strongly in the particle-phase composition as well.

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The disolvated proton, H(OH2)2+ is employed as a chemical reagent in low pressure (˂ 10-5 torr) investigations by ion cyclotron resonance spectroscopy. Since termolecular reactions are absent at low pressure, disolvated protons are not generally observed. However H(OH2)2+ is produced in a sequence of bimolecular reactions in mixtures containing H2O and one of a small number of organohalide precursors. Then a series of hydrated Lewis bases is produced by H3O+ transfer from H(OH2)2+. In Chapter II, the relative stability of hydrated bases containing heteroatoms of both first and second row elements is determined from the preferred direction of H3O+ transfer between BH(OH2)+ complexes. S and P containing bases are shown to bind H3O+ more weakly than O and N bases with comparable proton affinities. A simple model of hydrogen bonding is proposed to account for these observations.

H+ transfer from H(OH2)2+ to several Lewis bases also occurs at low pressure. In Chapter III the relative importance of H3O+ transfer and H+ transfer from H(OH2)2+ to a series of bases is observed to be a function of base strength. Beginning with CH3COOH, the weakest base for which H+ transfer is observed, the importance of H+ transfer increases with increasing proton affinity of the acceptor base. The nature of neutral products formed from H(OH2)2+ by loss of H+ is also considered.

Chapters IV and V deal with thermochemistry of small fluorocarbons determined by photoionization mass spectrometry. The enthalpy of formation of CF2 is considered in Chapter IV. Photoionization of perfluoropropylene, perfluorocyclopropane, and trifluoromethyl benzene yield onsets for ions formed by loss of a CF2 neutral fragment. Earlier determinations of ΔH°f298 (CF2) are reinterpreted using updated thermochemical values and compared with results of this study. The heat of formation of neutral perfluorocyclopropane is also derived. Finally, the energetics of interconversion of perfluoropropylene and perfluorocyclopropane are considered for both the neutrals and their molecular ions.

In Chapter V the heats of formation of CF3+ and CF3I+are derived from photoionization of CF3I. These are considered with respect to ion-molecule reactions observed in CF3I monitored by the techniques of ion cyclotron resonance spectroscopy. Results obtained in previous experiments are also compared.

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This thesis is in two parts. In the first section, the operator structure of the singular terms in the equal-time commutator of space and time components of the electromagnetic current is investigated in perturbation theory by establishing a connection with Feynman diagrams. It is made very plausible that the singular term is a c number. Some remarks are made about the same problem in the electrodynamics of a spinless particle.

In the second part, an SU(3) symmetric multi-channel calculation of the electromagnetic mass differences in the pseudoscalar meson and baryon octets is carried out with an attempt to include some of the physics of the crossed (pair annihilation) channel along the lines of the recent work by Ball and Zachariasen. The importance of the tensor meson Regge trajectories is emphasized. The agreement with experiment is poor for the isospin one mass differences, but excellent for those with isospin two.

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Mass transfer from wetted surfaces on one-inch cylinders with unwetted approach sections was studied experimentally by means of the evaporation of n-octane and n-heptane into an air stream in axisymmetrical flow, for Reynolds numbers from 5,000 to 310,000. A transition from the laminar to the turbulent boundary layer was observed to occur at Reynolds numbers from 10,000 to 15,000. The results were expressed in terms of the Sherwood number as a function of the Reynolds number, the Schmidt number, and the ratio of the unwetted approach length to the total length. Empirical formulas were obtained for both laminar and turbulent regimes. The rates of mass transfer obtained were higher than theoretical and experimental results obtained by previous investigators for mass and heat transfer from flat plates.

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Part I

The latent heat of vaporization of n-decane is measured calorimetrically at temperatures between 160° and 340°F. The internal energy change upon vaporization, and the specific volume of the vapor at its dew point are calculated from these data and are included in this work. The measurements are in excellent agreement with available data at 77° and also at 345°F, and are presented in graphical and tabular form.

Part II

Simultaneous material and energy transport from a one-inch adiabatic porous cylinder is studied as a function of free stream Reynolds Number and turbulence level. Experimental data is presented for Reynolds Numbers between 1600 and 15,000 based on the cylinder diameter, and for apparent turbulence levels between 1.3 and 25.0 per cent. n-heptane and n-octane are the evaporating fluids used in this investigation.

Gross Sherwood Numbers are calculated from the data and are in substantial agreement with existing correlations of the results of other workers. The Sherwood Numbers, characterizing mass transfer rates, increase approximately as the 0.55 power of the Reynolds Number. At a free stream Reynolds Number of 3700 the Sherwood Number showed a 40% increase as the apparent turbulence level of the free stream was raised from 1.3 to 25 per cent.

Within the uncertainties involved in the diffusion coefficients used for n-heptane and n-octane, the Sherwood Numbers are comparable for both materials. A dimensionless Frössling Number is computed which characterizes either heat or mass transfer rates for cylinders on a comparable basis. The calculated Frössling Numbers based on mass transfer measurements are in substantial agreement with Frössling Numbers calculated from the data of other workers in heat transfer.

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An experimental method combined with boundary layer theory is given for evaluating the added mass of a sphere moving along the axis of a circular cylinder filled with water or oil. The real fluid effects are separated from ideal fluid effects.

The experimental method consists essentially of a magnetic steel sphere propelled from rest by an electromagnetic coil in which the current is accurately controlled so that it only supplies force for a short time interval which is within the laminar flow regime of the fluid. The motion of the sphere as a function of time is recorded on single frame photographs using a short-arc multiple flash lamp with accurately controlled time intervals between flashes.

A concept of the effect of boundary layer displacement on the fluid flow around a sphere is introduced to evaluate the real fluid effects on the added mass. Surprisingly accurate agreement between experiment and theory is achieved.

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The Q values and 0o cross sections of (He3, n) reactions forming seven proton-rich nuclei have been measured with accuracies varying from 6 to 18 keV. The Q values (in keV) are: Si26 (85), S30 (-573), Ar34 (-759), Ti42 (-2865), Cr48 (5550), Ni56 (4513) and Zn60 (818). At least one excited state was found for all but Ti42. The first four nuclei complete isotopic spin triplets; the results obtained agree well with charge-symmetry predictions. The last three, all multiples of the α particle, are important in the α and e-process theories of nucleo-synthesis in stars. The energy available for β decay of these three was found by magnetic spectrometer measurements of the (He3, p) Q values of reactions leading to V48, Co56, and Cu60. Many excited states were seen: V48 (3), Co56 (15), Cu60 (23). The first two states of S30 are probably 0+ and 2+ from (He3, n) angular distribution measurements. Two NaI γ-ray measurements are described: the decay of Ar34 (measured Ƭ1/2 = 1.2 ± 0.3s) and the prompt γ-ray spectrum from Fe54(He3, nγ)Ni56. Possible collective structure in Ni56 and Ca40, both doubly magic, is discussed.

The (He3, n) neutron energy and yield measurements utilized neutron-induced nuclear reactions in a silicon semiconductor detector. Cross sections for the most important detection processes, Si28 (n, α) Mg25 and Si28 (n, p) Al28, are presented for reactions leading to the first four states of both residual nuclei for neutron energies from 7.3 to 16.4 MeV. Resolution and pulse-height anomalies associated with recoil Mg25 and Al28 ions are discussed. The 0o cross section for Be9 (α, n) C12, used to provide calibration neutrons, has been measured with a stilbene spectrometer for no (5.0 ≤ Eα ≤ 12 MeV), n1 (4.3 ≤ Eα ≤ 12.0 MeV) and n2 (6.0 ≤ Eα ≤ 10.1 MeV). Resonances seen in the no yield may correspond to nine new levels in C13.

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Kilometer scale interferometers for the detection of gravitational waves are currently under construction by the LIGO (Laser Interferometer Gravitational-wave Observatory) and VIRGO projects. These interferometers will consist of two Fabry-Perot cavities illuminated by a laser beam which is split in half by a beam splitter. A recycling mirror between the laser and the beam splitter will reflect the light returning from the beam splitter towards the laser back into the interferometer. The positions of the optical components in these interferometers must be controlled to a small fraction of a wavelength of the laser light. Schemes to extract signals necessary to control these optical components have been developed and demonstrated on the tabletop. In the large scale gravitational wave detectors the optical components must be suspended from vibration isolation platforms to achieve the necessary isolation from seismic motion. These suspended components present a new class of problems in controlling the interferometer, but also provide more exacting test of interferometer signal and noise models.

This thesis discusses the first operation of a suspended-mass Fabry-Perot-Michelson interferometer, in which signals carried by the optically recombined beams are used to detect and control all important mirror displacements. This interferometer uses an optical configuration and signal extraction scheme that is planned for the full scale LIGO interferometers with the simplification of the removal of the recycling mirror. A theoretical analysis of the performance that is expected from such an interferometer is presented and the experimental results are shown to be in generally good agreement.

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Recent theoretical developments in the reggeization of inelastic processes involving particles with high spin are incorporated into a model of vector meson production. A number of features of experimental differential cross sections and density matrices are interpreted in terms of this model.

The method chosen for reggeization of helicity amplitudes first separates kinematic zeros and singularities from the parity-conserving amplitudes and then applies results of Freedman and Wang on daughter trajectories to the remaining factors. Kinematic constraints on helicity amplitudes at t = 0 and t = (M – MΔ)2 are also considered.

It is found that data for reactions of types πN→VN and πN→VΔ are consistent with a model of this type in which all kinematic constraints at t = 0 are satisfied by evasion (vanishing of residue functions). As a quantitative test of the parametrization, experimental differential cross sections of vector meson production reactions dominated by pion trajectory exchange are compared with the theory. It is found that reduced residue functions are approximately constant, once the kinematic behavior near t = (M – MΔ)2 has been removed.

The alternative possibility of conspiracy between amplitudes is also discussed; and it is shown that unless conspiracy is present, some amplitudes allowed by angular momentum conservation will not contribute with full strength in the forward direction. An example, γp→π+n in which the data for dσ/dt indicate conspiracy, is studied in detail.