I. The rate and mechanism of the vapor-phase reaction between water and parts-per-million concentrations of nitrogen dioxide. II. The rate and mechanism of the air oxidation of parts-per-million concentrations of nitric oxide in the presence of water vapor.

Part I

A study of the thermal reaction of water vapor and parts-per-million concentrations of nitrogen dioxide was carried out at ambient temperature and at atmospheric pressure. Nitric oxide and nitric acid vapor were the principal products. The initial rate of disappearance of nitrogen dioxide was first order with respect to water vapor and second order with respect to nitrogen dioxide. An initial third-order rate constant of 5.5 (± 0.29) x 10⁴ liter² mole^-2 sec^-1 was found at 25˚C. The rate of reaction decreased with increasing temperature. In the temperature range of 25˚C to 50˚C, an activation energy of -978 (± 20) calories was found.

The reaction did not go to completion. From measurements as the reaction approached equilibrium, the free energy of nitric acid vapor was calculated. This value was -18.58 (± 0.04) kilocalories at 25˚C.

The initial rate of reaction was unaffected by the presence of oxygen and was retarded by the presence of nitric oxide. There were no appreciable effects due to the surface of the reactor. Nitric oxide and nitrogen dioxide were monitored by gas chromatography during the reaction.

Part II

The air oxidation of nitric oxide, and the oxidation of nitric oxide in the presence of water vapor, were studied in a glass reactor at ambient temperatures and at atmospheric pressure. The concentration of nitric oxide was less than 100 parts-per-million. The concentration of nitrogen dioxide was monitored by gas chromatography during the reaction.

For the dry oxidation, the third-order rate constant was 1.46 (± 0.03) x 10⁴ liter² mole^-2 sec^-1 at 25˚C. The activation energy, obtained from measurements between 25˚C and 50˚C, was -1.197 (±0.02) kilocalories.

The presence of water vapor during the oxidation caused the formation of nitrous acid vapor when nitric oxide, nitrogen dioxide and water vapor combined. By measuring the difference between the concentrations of nitrogen dioxide during the wet and dry oxidations, the rate of formation of nitrous acid vapor was found. The third-order rate constant for the formation of nitrous acid vapor was equal to 1.5 (± 0.5) x 10⁵ liter² mole^-2 sec^-1 at 40˚C. The reaction rate did not change measurably when the temperature was increased to 50˚C. The formation of nitric acid vapor was prevented by keeping the concentration of nitrogen dioxide low.

Surface effects were appreciable for the wet tests. Below 35˚C, the rate of appearance of nitrogen dioxide increased with increasing surface. Above 40˚C, the effect of surface was small.

Mechanistic studies of a model reaction for enzymatic hydroxylation

A study has been made of the reaction mechanism of a model system for enzymatic hydroxylation. The results of a kinetic study of the hydroxylation of 2-hydroxyazobenzene derivatives by cupric ion and hydrogen peroxide are presented. An investigation of kinetic orders indicates that hydroxylation proceeds by way of a coordinated intermediate complex consisting of cupric ion and the mono anions of 2-hydroxyazobenzene and hydrogen peroxide. Studies with deuterated substrate showed the absence of a primary kinetic isotope effect and no evidence of an NIH shift. The effect of substituents on the formation of intermediate complexes and the overall rate of hydroxylation was studied quantitatively in aqueous solution. The combined results indicate that the hydroxylation step is only slightly influenced by ring substitution. The substituent effect is interpreted in terms of reaction by a radical path or a concerted mechanism in which the formation of ionic intermediates is avoided. The reaction mechanism is discussed as a model for enzymatic hydroxylation.

Heterometallic Complexes as Models of Enzymatic Active Sites

This dissertation describes studies on two multinucleating ligand architectures: the first scaffold was designed to support tricopper complexes, while the second platform was developed to support tri- and tetrametallic clusters.

In Chapter 2, the synthesis of yttrium (and lanthanide) complexes supported by a tripodal ligand framework designed to bind three copper centers in close proximity is described. Tricopper complexes were shown to react with dioxygen in a 1:1 [Cu₃]/O₂ stoichiometry to form intermediates in which the O–O bond was fully cleaved, as characterized via UV-Vis spectroscopy and determination of the reaction stoichiometry. Pre-arrangement of the three Cu centers was pivotal to cooperative O₂ activation, as mono-copper complexes reacted differently with dioxgyen. The reactivity of the observed intermediates was studied with various substrates (reductants, O-atom acceptors, H-atom donors, Brønsted acids) to determine their properties. In Chapter 3, the reactivity of the same yttrium-tricopper complex with nitric oxide was explored. Reductive coupling to form a trans-hyponitrite complex (characterized by X-ray crystallography) was observed via cooperative reactivity by an yttrium and a copper center on two distinct tetrametallic units. The hyponitrite complex was observed to release nitrous oxide upon treatment with a Brønsted acid, supporting its viability as an intermediate in nitric oxide reduction to nitrous oxide.

In Chapter 4, a different multinucleating ligand scaffold was employed to synthesize heterometallic triiron clusters containing one oxide and one hydroxide bridges. The effects of the redox-inactive, Lewis acidic heterometals on redox potential was studied by cyclic voltammetry, unveiling a linear correlation between redox potential and heterometal Lewis acidity. Further studies on these complexes showed that the Lewis acidity of the redox-inactive metals also affected the oxygen-atom transfer reactivity of these clusters. Comparisons of this reactivity with manganese systems, collaborative efforts to reassign the structures of related manganese oxo-hydroxo clusters, and synthetic attempts to access related dioxo clusters are also described.

In Appendix A, ongoing efforts to synthesize new clusters supported by the same multinucleating ligand platform are described. Studies of novel approaches towards ligand exchange in tetrametallic clusters and incorporation of new supporting and bridging ligand motifs in trinuclear complexes are presented.

An investigation of the three-body reaction He^3(He^3, 2p)He^4

Reactions produced by the He³ bombardment of the He³ have been investigated for bombarding energies from 1 to 20 MeV using a tandem Van de Graaff accelerator. Proton spectra from the three-body reaction He³(He³, 2p)He⁴ have been measured with a counter telescope at 13 angles for 9 bombarding energies between 3 and 18 MeV. The results are compared with a model for the reaction which includes a strong p-He⁴ final-state interaction. Alpha-particle spectra have been obtained at 12 and 18 MeV for forward angles with a magnetic spectrometer. These spectra indicate a strongly forward-peaked mechanism involving the ¹S₀ p-p interaction in addition to the p-He⁴ interaction. Measurements of p-He⁴ and p-p coincidence spectra at 10 MeV confirm these features of the reaction mechanism. Deuteron spectra from the reaction of He³(He³, d)pHe³ have been measured at 18 MeV. A triton spectrum from the reaction He³(He³, t)3p at 20 MeV and 4⁰ is interpreted in terms of a sequential decay through an excited state of the alpha particle at 20.0 MeV. No effects are observed which would indicate an interaction in the residual (3p) system. Below 3 MeV the He³(He³, 2p)He⁴ reaction mechanism is observed to be changing and further measurements are suggested in view of the importance of this reaction in stellar interiors.

Total cross section measurements for ^3He(^3He, 2p)^4He at low energies

Precise measurements of the total reaction cross section for ³He(³He,2p)⁴He He have been made in the range of center-of-mass energies between 1100 keV and 80 keV. A differentially pumped gas target modified to operate with a limited quantity of the target gas was employed to minimize the uncertainties in the primary energy and energy straggle. Beam integration inside the target gas was carried out by a calorimetric device which measures the total energy spent in a heat sink rather than the total charge in a Faraday cup. Proton energy spectra have been obtained using a counter telescope consisting of a gas proportional counter and a surface barrier detector and angular distributions of these protons have been measured at seven bombarding energies. Cross section factors, S(E), have been calculated from the total cross sections and fitted to a linear function of energy over different ranges of energy. For E_cm < 500 keV

S(E_cm) = S₀ + S₁ E_cm

where S₀ = (5.0 ^+0.6_-0.4) MeV - barns and S₁ = (-1.8 ± 0.5) barns.

The reduced-alpha-width of the lowest 1¯ state of ^(16)O

Cross sections for the reaction ¹²C(α,γ)¹⁶O have been measured for a range of center-of-mass alpha particle energies extending from 1.72 MeV to 2.94 MeV. Two 8"x5" NaI (Tℓ) crystals were used to detect gamma rays; time-of-flight technique was employed to suppress cosmic ray background and background due to neutrons arising mainly from the ¹³C(α,n)¹⁶O reaction. Angular distributions were measured at center-of-mass alpha energies of 2.18, 2.42, 2.56 and 2.83 MeV. Upper limits were placed on the amount of radiation cascading through the 6.92 or 7.12-MeV states in ¹⁶O. By means of theoretical fits to the measured electric dipole component of the total cross section, in which interference between the 1¯ states in ¹⁶O at 7.12 MeV and at 9.60 MeV is taken into account, it is possible to extract the dimensionless, reduced-alpha-width of the 7.12-MeV state in ¹⁶O. A three-level R-matrix parameterization of the data yields the width Θ_α,F² = 0.14^+0.10_-0.08. A "hybrid" R-matrix-optical-model parameterization yields Θ_α,F² = 0.11^+0.11_-0.07. This quantity is of crucial importance in determining the abundances of ¹²C and ¹⁶O at the end of helium burning in stars.

Applications of a nuclear technique for depth-sensitive hydrogen analysis : trapped H in lunar samples and the hydration of terrestrial obsidian

The resonant nuclear reaction ¹⁹F(p,αy)¹⁶O has been used to perform depth-sensitive analyses for both fluorine and hydrogen in solid samples. The resonance at 0.83 MeV (center-of-mass) in this reaction has been applied to the measurement of the distribution of trapped solar protons in lunar samples to depths of ~1/2µm. These results are interpreted in terms of a redistribution of the implanted H which has been influenced by heavy radiation damage in the surface region. Fluorine determinations have been performed in a 1-µm surface layer on lunar and meteoritic samples using the same ¹⁹F(p,αy)¹⁶O resonance. The measurement of H depth distributions has also been used to study the hydration of terrestrial obsidian, a phenomenon of considerable archaeological interest as a means of dating obsidian artifacts. Additional applications of this type of technique are also discussed.

An experimental study of a stellar neutron source: ^(13)C(α, n)^(16)O

Described in this thesis are measurements made of the thick-target neutron yield from the reaction ¹³C(α, n)¹⁶O. The yield was determined for laboratory bombarding energies between 0.475 and 0.700 MeV, using a stilbene crystal neutron detector and pulse-shape discrimination to eliminate gamma rays. Stellar temperatures between 2.5 and 4.5 x 10^{8 o}K are involved in this energy region. From the neutron yield was extracted the astrophysical cross-section factor S(E), which was found to fit a linear function: S(E) = [(5.48 ± 1.77) + (12.05 ± 3.91)E] x 10⁵ MeV-barns, center-of-mass system. The stellar rate of the ¹³C(α, n)¹⁶O reaction if calculated, and discussed with reference to helium burning and neutron production in the core of a giant star.

Results are also presented of measurements carried out on the reaction ⁹Be(α, n)¹²C, taken with a thin Be target. The bombarding energy-range covered was from 0.340 to 0.680 MeV, with excitation curves for the ground- and first excited-state neutrons being reported. Some angular distributions were also measured. Resonances were found at bombarding energies of E_LAB = 0.520 MeV (E_CM = 0.360 MeV, Γ ~ 55 keV CM, ωγ = 3.79 eV CM) and E_LAB = 0.600 MeV (E_CM = 0.415 MeV, Γ ˂ 4 keV CM, ωγ = 0.88 eV CM). The astrophysical rate of the ⁹Be(α, n)¹²C reaction due to these resonances is calculated.

The Marine Science Library, Resource Center : poster presentation

The first concept of a new library was introduced in 2001 by a faculty member at the University of Texas Marine Science Institute. The suggestion for the construction of a new library was based on two specific reasons: existing library is located in one of the most vulnerable buildings to hurricane damage and the library has outgrown its current space. This presentation provides a general overview of the current status and changing needs of the Marine Science Library and how the idea of a new library finally became a reality

Experimental study study of antiproton-proton annihilation into a pair of charged Pi-Mesons or K-Mesons for incident antiproton mementa in the range from 0.72 GeV/c to 2.62 GeV/c

The cross sections for the two antiproton-proton annihilation-in-flight modes,

ˉp + p → π⁺ + π^-

ˉp + p → k⁺ + k^-

were measured for fifteen laboratory antiproton beam momenta ranging from 0.72 to 2.62 GeV/c. No magnets were used to determine the charges in the final state. As a result, the angular distributions were obtained in the form [dσ/dΩ (Θ_C.M.) + dσ/dΩ (π – Θ_C.M.)] for 45 ≲ Θ_C.M. ≲ 135°.

A hodoscope-counter system was used to discriminate against events with final states having more than two particles and antiproton-proton elastic scattering events. One spark chamber was used to record the track of each of the two charged final particles. A total of about 40,000 pictures were taken. The events were analyzed by measuring the laboratory angle of the track in each chamber. The value of the square of the mass of the final particles was calculated for each event assuming the reaction

ˉp + p → a pair of particles with equal masses.

About 20,000 events were found to be either annihilation into π ^±-pair or k ^±-pair events. The two different charged meson pair modes were also distinctly separated.

The average differential cross section of ˉp + p → π⁺ + π^- varied from ~ 25 µb/sr at antiproton beam momentum 0.72 GeV/c (total energy in center-of-mass system, √s = 2.0 GeV) to ~ 2 µb/sr at beam momentum 2.62 GeV/c (√s = 2.64 GeV). The most striking feature in the angular distribution was a peak at Θ_C.M. = 90° (cos Θ_C.M. = 0) which increased with √s and reached a maximum at √s ~ 2.1 GeV (beam momentum ~ 1.1 GeV/c). Then it diminished and seemed to disappear completely at √s ~ 2.5 GeV (beam momentum ~ 2.13 GeV/c). A valley in the angular distribution occurred at cos Θ_C.M. ≈ 0.4. The differential cross section then increased as cos Θ_C.M. approached 1.

The average differential cross section for ˉp + p → k⁺ + k^- was about one third of that of the π^±-pair mode throughout the energy range of this experiment. At the lower energies, the angular distribution, unlike that of the π^±-pair mode, was quite isotropic. However, a peak at Θ_C.M. = 90° seemed to develop at √s ~ 2.37 GeV (antiproton beam momentum ~ 1.82 GeV/c). No observable change was seen at that energy in the π^±-pair cross section.

The possible connection of these features with the observed meson resonances at 2.2 GeV and 2.38 GeV, and its implications, were discussed.

I. Quantum mechanics of one-dimensional two-particle models. II. A quantum mechanical treatment of inelastic collisions

Part I

Solutions of Schrödinger’s equation for system of two particles bound in various stationary one-dimensional potential wells and repelling each other with a Coulomb force are obtained by the method of finite differences. The general properties of such systems are worked out in detail for the case of two electrons in an infinite square well. For small well widths (1-10 a.u.) the energy levels lie above those of the noninteresting particle model by as much as a factor of 4, although excitation energies are only half again as great. The analytical form of the solutions is obtained and it is shown that every eigenstate is doubly degenerate due to the “pathological” nature of the one-dimensional Coulomb potential. This degeneracy is verified numerically by the finite-difference method. The properties of the square-well system are compared with those of the free-electron and hard-sphere models; perturbation and variational treatments are also carried out using the hard-sphere Hamiltonian as a zeroth-order approximation. The lowest several finite-difference eigenvalues converge from below with decreasing mesh size to energies below those of the “best” linear variational function consisting of hard-sphere eigenfunctions. The finite-difference solutions in general yield expectation values and matrix elements as accurate as those obtained using the “best” variational function.

The system of two electrons in a parabolic well is also treated by finite differences. In this system it is possible to separate the center-of-mass motion and hence to effect a considerable numerical simplification. It is shown that the pathological one-dimensional Coulomb potential gives rise to doubly degenerate eigenstates for the parabolic well in exactly the same manner as for the infinite square well.

Part II

A general method of treating inelastic collisions quantum mechanically is developed and applied to several one-dimensional models. The formalism is first developed for nonreactive “vibrational” excitations of a bound system by an incident free particle. It is then extended to treat simple exchange reactions of the form A + BC →AB + C. The method consists essentially of finding a set of linearly independent solutions of the Schrödinger equation such that each solution of the set satisfies a distinct, yet arbitrary boundary condition specified in the asymptotic region. These linearly independent solutions are then combined to form a total scattering wavefunction having the correct asymptotic form. The method of finite differences is used to determine the linearly independent functions.

The theory is applied to the impulsive collision of a free particle with a particle bound in (1) an infinite square well and (2) a parabolic well. Calculated transition probabilities agree well with previously obtained values.

Several models for the exchange reaction involving three identical particles are also treated: (1) infinite-square-well potential surface, in which all three particles interact as hard spheres and each two-particle subsystem (i.e. BC and AB) is bound by an attractive infinite-square-well potential; (2) truncated parabolic potential surface, in which the two-particle subsystems are bound by a harmonic oscillator potential which becomes infinite for interparticle separations greater than a certain value; (3) parabolic (untruncated) surface. Although there are no published values with which to compare our reaction probabilities, several independent checks on internal consistency indicate that the results are reliable.

Part I. Coenzyme B12 as a hydroformylation-type catalyst. Part II. Mechanisms of hydrogen transfer in the methylmalonyl coenzyme a mutase reaction

Part I

The mechanism of the hydroformylation reaction was studied. Using cobalt deuterotetracarbonyl and 1-pentene as substrates, the first step in the reaction, addition of cobalt tetracarbonyl to an olefin, was shown to be reversible.

Part II

The role of coenzyme B₁₂ in the isomerization of methylmalonyl coenzyme A to succinyl coenzyme A by methylmalonyl coenzyme A mutase was studied. The reaction was allowed to proceed to partial completion using a mixture of methylmalonyl coenzyme A and 4, 4, 4-tri-²H-methylmalonyl coenzyme A as substrate. The deuterium distribution in the product, succinyl coenzyme A, was shown to best fit a model in which hydrogen is transferred from C-4 of methylmalonyl coenzyme A to C-5’ of the adenosyl moiety of coenzyme B₁₂ in the rate determining step. The three hydrogens at the 5’-adenosyl position of the coenzyme B₁₂ intermediate are then able to become enzymatically equivalent before hydrogen is transferred from the coenzyme B₁₂ intermediate to form succinyl coenzyme A.

Invertible dark-center diffraction of the metal film induced by femtosecond laser

We found reversible dark-center diffraction of the transmitted probe beam passing through the chromium film. which is induced by the pump femtosecond laser. The dark-center diffraction of I he transmitted probe beam appears and disappears with and without the pump beam. A view of diffractive optics with binary phase plate is put forward, which explains the reversible dark-center diffractive optical phenomenon. The pre-ablated hole on the metal film can be regarded as a uniform light filed without phase modulation, the Surrounding Circular part around the pre-ablated hole can be regarded as "phase modulated". Therefore, this diffraction optic view might be helpful for us to understand the phase change of the metal film introduced by the femtosecond laser pulse. (C) 2008 Elsevier B.V, All rights reserved.

An investigation of the reaction negative K¯p → K¯π⁺ at P_(lab) = 2 Gev/c

The reaction K^-p→K^-π⁺n has been studied for incident kaon momenta of 2.0 GeV/c. A sample of 19,881 events was obtained by a measurement of film taken as part of the K-63 experiment in the Berkeley 72 inch bubble chamber.

Based upon our analysis, we have reached four conclusions. (1) The magnitude of the extrapolated Kπ cross section differs by a factor of 2 from the P-wave unitarity prediction and the K⁺n results; this is probably due to absorptive effects. (2) Fits to the moments yield precise values for the Kπ S-wave which agree with other recent statistically accurate experiments. (3) An anomalous peak is present in our backward K^-p→(π+n) K^- u-distribution. (4) We find a non-linear enhancement due to interference similiar to the one found by Bland et al. (Bland 1966).