38 resultados para Excited states
em CaltechTHESIS
Resumo:
PART I
The energy spectrum of heavily-doped molecular crystals was treated in the Green’s function formulation. The mixed crystal Green’s function was obtained by averaging over all possible impurity distributions. The resulting Green’s function, which takes the form of an infinite perturbation expansion, was further approximated by a closed form suitable for numerical calculations. The density-of-states functions and optical spectra for binary mixtures of normal naphthalene and deuterated naphthalene were calculated using the pure crystal density-of-state functions. The results showed that when the trap depth is large, two separate energy bands persist, but when the trap depth is small only a single band exists. Furthermore, in the former case it was found that the intensities of the outer Davydov bands are enhanced whereas the inner bands are weakened. Comparisons with previous theoretical calculations and experimental results are also made.
PART II
The energy states and optical spectra of heavily-doped mixed crystals are investigated. Studies are made for the following binary systems: (1) naphthalene-h8 and d8, (2) naphthalene--h8 and αd4, and (3) naphthalene--h8 and βd1, corresponding to strong, medium and weak perturbations. In addition to ordinary absorption spectra at 4˚K, band-to-band transitions at both 4˚K and 77˚K are also analyzed with emphasis on their relations to cooperative excitation and overall density-of-states functions for mixed crystals. It is found that the theoretical calculations presented in a previous paper agree generally with experiments except for cluster states observed in system (1) at lower guest concentrations. These features are discussed semi-quantitatively. As to the intermolecular interaction parameters, it is found that experimental results compare favorably with calculations based on experimental density-of-states functions but not with those based on octopole interactions or charge-transfer interactions. Previous experimental results of Sheka and the theoretical model of Broude and Rashba are also compared with present investigations.
PART III
The phosphorescence, fluorescence and absorption spectra of pyrazine-h4 and d4 have been obtained at 4˚K in a benzene matrix. For comparison, those of the isotopically mixed crystal pyrazine-h4 in d4 were also taken. All these spectra show extremely sharp and well-resolved lines and reveal detailed vibronic structure.
The analysis of the weak fluorescence spectrum resolves the long-disputed question of whether one or two transitions are involved in the near-ultraviolet absorption of pyrazine. The “mirror-image relationship” between absorption and emission shows that the lowest singlet state is an allowed transition, properly designated as 1B3u ← 1A1g. The forbidden component 1B2g, predicted by both “exciton” and MO theories to be below the allowed component, must lie higher. Its exact location still remains uncertain.
The phosphorescence spectrum when compared with the excitation phosphorescence spectra, indicates that the lowest triplet state is also symmetry allowed, showing a strong 0-0 band and a “mirror-image relationship” between absorption and emission. In accordance with previous work, the triplet state is designated as 3B3u.
The vibronic structure of the phosphorescence spectrum is very complicated. Previous work on the analysis of this spectrum all concluded that a long progression of v6a exists. Under the high resolution attainable in our work, the supposed v6a progression proves to have a composite triplet structure, starting from the second member of the progression. Not only is the v9a hydrogen-bending mode present as shown by the appearance of the C-D bending mode in the d4 spectrum, but a band of 1207 cm-1 in the pyrazine in benzene system and 1231 cm-1 in the mixed crystal system is also observed. This band is assigned as 2v6b and of a1g symmetry. Its anonymously strong intensity in the phosphorescence spectrum is interpreted as due to the Fermi resonance with the 2v6a and v9a band.
To help resolve the present controversy over the crystal phosphorescence spectrum of pyrazine, detailed vibrational analyses of the emission spectra were made. The fluorescence spectrum has essentially the same vibronic structure as the phosphorescence spectrum.
Resumo:
Part I of this thesis deals with 3 topics concerning the luminescence from bound multi-exciton complexes in Si. Part II presents a model for the decay of electron-hole droplets in pure and doped Ge.
Part I.
We present high resolution photoluminescence data for Si doped With Al, Ga, and In. We observe emission lines due to recombination of electron-hole pairs in bound excitons and satellite lines which have been interpreted in terms of complexes of several excitons bound to an impurity. The bound exciton luminescence in Si:Ga and Si:Al consists of three emission lines due to transitions from the ground state and two low lying excited states. In Si:Ga, we observe a second triplet of emission lines which precisely mirror the triplet due to the bound exciton. This second triplet is interpreted as due to decay of a two exciton complex into the bound exciton. The observation of the second complete triplet in Si:Ga conclusively demonstrates that more than one exciton will bind to an impurity. Similar results are found for Si:Al. The energy of the lines show that the second exciton is less tightly bound than the first in Si:Ga. Other lines are observed at lower energies. The assumption of ground state to ground-state transitions for the lower energy lines is shown to produce a complicated dependence of binding energy of the last exciton on the number of excitons in a complex. No line attributable to the decay of a two exciton complex is observed in Si:In.
We present measurements of the bound exciton lifetimes for the four common acceptors in Si and for the first two bound multi-exciton complexes in Si:Ga and Si:Al. These results are shown to be in agreement with a calculation by Osbourn and Smith of Auger transition rates for acceptor bound excitons in Si. Kinetics determine the relative populations of complexes of various sizes and work functions, at temperatures which do not allow them to thermalize with respect to one another. It is shown that kinetic limitations may make it impossible to form two-exciton complexes in Si:In from a gas of free excitons.
We present direct thermodynamic measurements of the work functions of bound multi-exciton complexes in Al, B, P and Li doped Si. We find that in general the work functions are smaller than previously believed. These data remove one obstacle to the bound multi-exciton complex picture which has been the need to explain the very large apparent work functions for the larger complexes obtained by assuming that some of the observed lines are ground-state to ground-state transitions. None of the measured work functions exceed that of the electron-hole liquid.
Part II.
A new model for the decay of electron-hole-droplets in Ge is presented. The model is based on the existence of a cloud of droplets within the crystal and incorporates exciton flow among the drops in the cloud and the diffusion of excitons away from the cloud. It is able to fit the experimental luminescence decays for pure Ge at different temperatures and pump powers while retaining physically reasonable parameters for the drops. It predicts the shrinkage of the cloud at higher temperatures which has been verified by spatially and temporally resolved infrared absorption experiments. The model also accounts for the nearly exponential decay of electron-hole-droplets in lightly doped Ge at higher temperatures.
Resumo:
The two lowest T = 3/2 levels in 21Na have been studied in the 19F(3He, n), 20Ne (p,p) and 20Ne (p,p’) reactions, and their excitation energies, spins, parities and widths have been determined. In a separate investigation, branching ratios were measured for the isospin-nonconserving particle decays of the lowest T = 3/2 levels in 17O and 17F to the ground state and first two excited states of 16O, by studying the 15N(3He,n) 17F*(p) 16O and 18O(3He, α)17O*(n) 16O reactions.
The 19F(3He,n) 21Na reaction was studied at incident energies between 4.2 and 5.9 MeV using a pulsed-beam neutron-time-of-flight spectrometer. Two T = 3/2 levels were identified at excitation energies of 8.99 ± 0.05 MeV (J > ½) and 9.22 ± 0.015 MeV (J π = ½+, Γ ˂ 40 keV). The spins and parities were determined by a comparison of the measured angular distributions with the results of DWBA calculations.
These two levels were also obsesrved as isospin-forbidden resonances in the 20Ne(p,p) and 20Ne(p,p’) reactions. Excitation energies were measured and spins, parities, and widths were determined from a single level dispersion theory analysis. The following results were obtained:
Ex = 8.973 ± 0.007 MeV, J π = 5/2 + or 3/2+, Γ ≤ 1.2 keV,
Γpo = 0.1 ± 0.05 keV; Ex = 9.217 ± 0.007 MeV, Jπ = ½ +,
Γ = 2.3 ± 0.5 keV, Γpo = 1.1 ± 0.3 keV.
Isospin assignments were made on the basis of excitation energies, spins, parities, and widths.
Branching ratios for the isospin-nonconserving proton decays of the 11.20 MeV, T = 3/2 level in 17F were measured by the 15N(3He,n) 17 F*(p) 16O reaction to be 0.088 ± 0.016 to the ground state of 16O and 0.22 ± 0.04 to the unresolved 6.05 and 6.13 MeV levels of 16O. Branching ratios for the neutron decays of the analogous T = 3/2 level, at 11.08 MeV in 17O, were measured by the 16O(3He, α)17O*(n)16O reaction to be 0.91 ± 0.15 to the ground state of 16O and 0.05 ± 0.02 to the unresolved 6.05 and 6.13 MeV states. By comparing the ratios of reduced widths for the mirror decays, the form of the isospin impurity in the T = 3/2 levels is shown to depend on Tz.
Resumo:
This dissertation presents the results of studies of several rotationally- resolved resonance enhanced multiphoton ionization (REMPI) processes in some simple molecular systems. The objective of these studies is to quantitatively identify the underlying dynamics of this highly state-specific process which utilizes the narrow bandwidth radiation of a laser to ionize a molecule by first preparing an excited state via multiphoton absorption and subsequently ionizing that state before it can decay. Coupled with high-resolution photoelectron spectroscopy, REMPI is clearly an important probe of molecular excited states and their photoioniza tion dynamics.
A key feature of our studies is that they are carried out using accurate Hartree-Fock orbitals to describe the photoelectron orbitals of the molecular ions. The use of such photoelectron orbitals is important in rotationally-resolved studies where the angular momentum coupling in the photoelectron orbital plays a significant role in the photoionization dynamics. In these studies the Hartree-Fock molecular molecular photoelectron orbitals are obtained by numerical solution of a Lippmann-Schwinger integral equation.
Studies reported here include investigations of (i) ionic rotational branching ratios and their energy dependence for REMPI via the A^2Σ^+(3sσ) and D^2Σ^+(3pσ)states of NO, (ii) the influence of angular momentum constraints on branching ratios at low photoelectron energies for REMPI via low-J levels of the resonant intermediate state, (iii) the strong dependence of photoelectron angular distributions on final ionic rotational state and on the alignment in REMPI of the A^2Σ^+ state of NO, (iv) vibrational state dependence of ionic rotational branching ratios arising from rapid orbital evolution in resonant states (E'^2Σ^+(3pσ) of CH), (v) the influence of rovibronic interactions on the rotational branching ratios seen in REMPI via the D^2Σ^+(3pσ) state of NO, and (vi) effects of laser intensity on the photoionization dynamics of REMPI.
Resumo:
The reaction 32S(3He, α) 31S has been used to locate 42 levels in 31S. For 11 of the first 17 levels ℓn-values have been determined. The first 6 excited states of 31S have been studied by applying the particle-gamma correlation method of Litherland and Ferguson (their Method II) to the reaction 32S(3He, αγ) 31S. The resulting spins and parities are: EX, Jπ = 1.25 MeV, 3/2+; 2.23 MeV, 5/2+; 3.08 MeV, 1/2+; 3.29 MeV, 5/2+, 3/2+; 3.35 MeV, 7/2, 3/2; 3.44 MeV, 3/2+. Mixing and branching ratios have also been determined. The ground state Q-value for the reaction 32S(3He, α)31S has been measured to be 5.538 ± 0.006 MeV. Analysis of the spectra of the reaction 32S(3He, α)33Cl which were obtained as a by-product of the spectra of the reaction 32S(3He, α) 31S located levels in 33Cl at the following excitation energies: 0, 810 ± 9, (1978 ± 14), 2351 ± 9, 2686 ± 8, 2848 ± 9 (a known doublet), 2980 ± 9, and 4119 ± 10 keV. The 2.0 MeV level was only weakly populated, and to confirm its existence the reaction 36Ar(p, α)33Cl has been studied. In this reaction the 2.0 MeV level was strongly populated and the measured excitation energy was 1999 ± 20 keV. The experimental results for 31S and 33Cl are compared with their analogs and with nuclear model predictions.
Resumo:
An automatic experimental apparatus for perturbed angular correlation measurements, capable of incorporating Ge(Li) detectors as well as scintillation counters, has been constructed.
The gamma-gamma perturbed angular correlation technique has been used to measure magnetic dipole moments of several nuclear excited states in the osmium transition region. In addition, the hyperfine magnetic fields, experienced by nuclei of 'impurity' atoms embedded in ferromagnetic host lattices, have been determined for several '4d' and '5d' impurity atoms.
The following magnetic dipole moments were obtained in the osmium transition region μ2+(190Os) = 0.54 ± 0.06 nm μ4+(190Os) = 0.88 ± 0.48 nm μ2+(192Os) = 0.56 ± 0.08 nm μ2+(192Pt) = 0.56 ± 0.06 nm μ2+’(192Pt) = 0.62 ± 0.14 nm.
These results are discussed in terms of three collective nuclear models; the cranking model, the rotation-vibration model and the pairing-plus-quadrupole model. The measurements are found to be in satisfactory agreement with collective descriptions of low lying nuclear states in this region.
The following hyperfine magnetic fields of 'impurities' in ferromagnetic hosts were determined; Hint(Cd Ni) = - (64.0 ± 0.8)kG Hint(Hg Fe) = - (440 ± 105)kG Hint(Hg Co) = - (370 ± 78)kG Hint(Hg Ni) = - (86 ± 22)kG Hint(Tl Fe) = - (185 ± 70)kG Hint(Tl Co) = - (90 ± 35)kG Hint(Ra Fe) = - (105 ± 20)kG Hint(Ra Co) = - (80 ± 16)kG Hint(Ra Ni) = - (30 ± 10)kG, where in Hint(AB); A is the impurity atom embedded in the host lattice B. No quantitative theory is available for comparison. However, these results are found to obey the general systematics displayed by these fields. Several mechanisms which may be responsible for the appearance of these fields are mentioned.
Finally, a theoretical expression for time-differential perturbed angular correlation measurement, which duplicates experimental conditions is developed and its importance in data analysis is discussed.
Resumo:
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.
Resumo:
The reaction 7Li(3He, p)9Be has been used to measure excitations and intrinsic widths of levels in 9Be below the 7Li + d threshold. Previously unreported levels have been found at excitations of (13.78 ± .03) MeV and (16.671 ± .008) MeV with widths of (590 ± 60) keV and (41 ± 4) keV respectively. Two overlapping levels have been found at (11.81 ± .02) MeV and (11.29 ± .03) MeV with widths of (400 ± 30) keV and (620 ± 70) keV respectively. Branching ratios from 9Be levels populated in this reaction to the ground and first excited states of 8Be have been measured by observing the associated protons in coincidence with the decay neutrons. Branching ratios were found to be:
Excitation in 9Be .... Branching Ratio.......... Final Nucleus.........
(MeV) .......................... (percent) .....................................
.. 2.43 ........................... 7.5 ± 1.5 .............. 8Be(g.s.)
.. 3.03 ........................... 87 ± 13......................................
.. 4.65 ........................... 13 ± 4.......................................
.. 6.76 .............................. ≤ 2 ......................................
.. 11.29 ...............................≤ 2 ......................................
.. 11.81 ...............................≤ 3 ......................................
.. 6.76 ........................... .41 ≤ B.R. ≤ .69 ....... 8Be(2+)
.. 11.29 ........................... 14 ± 4 .......................................
.. 11.81 ........................... 12 ± 4 .......................................
Corresponding reduced widths for neutron emission are calculated and a comparison of the results with the expectations of current nuclear models is made. In particular the measured branching ratio to 8Be(g.s.) from 9Be(2.43 MeV) corresponds to an f-wave reduced with θ2f = 2.1 x 10-2, in units of ħ2/mR2, with R = 4.35 fm. A comparison of this value with that predicted by a Nilsson model calculation, in which 9Be is taken to be a deformed nucleus, is discussed. The measured value for θ2f is found to be consistent with that expected on the basis of measured E2-transition rates between rotational levels in 9Be.
Resumo:
In the first part of the study, an RF coupled, atmospheric pressure, laminar plasma jet of argon was investigated for thermodynamic equilibrium and some rate processes.
Improved values of transition probabilities for 17 lines of argon I were developed from known values for 7 lines. The effect of inhomogeneity of the source was pointed out.
The temperatures, T, and the electron densities, ne , were determined spectroscopically from the population densities of the higher excited states assuming the Saha-Boltzmann relationship to be valid for these states. The axial velocities, vz, were measured by tracing the paths of particles of boron nitride using a three-dimentional mapping technique. The above quantities varied in the following ranges: 1012 ˂ ne ˂ 1015 particles/cm3, 3500 ˂ T ˂ 11000 °K, and 200 ˂ vz ˂ 1200 cm/sec.
The absence of excitation equilibrium for the lower excitation population including the ground state under certain conditions of T and ne was established and the departure from equilibrium was examined quantitatively. The ground state was shown to be highly underpopulated for the decaying plasma.
Rates of recombination between electrons and ions were obtained by solving the steady-state equation of continuity for electrons. The observed rates were consistent with a dissociative-molecular ion mechanism with a steady-state assumption for the molecular ions.
In the second part of the study, decomposition of NO was studied in the plasma at lower temperatures. The mole fractions of NO denoted by xNO were determined gas-chromatographically and varied between 0.0012 ˂ xNO ˂ 0.0055. The temperatures were measured pyrometrically and varied between 1300 ˂ T ˂ 1750°K. The observed rates of decomposition were orders of magnitude greater than those obtained by the previous workers under purely thermal reaction conditions. The overall activation energy was about 9 kcal/g mol which was considerably lower than the value under thermal conditions. The effect of excess nitrogen was to reduce the rate of decomposition of NO and to increase the order of the reaction with respect to NO from 1.33 to 1.85. The observed rates were consistent with a chain mechanism in which atomic nitrogen and oxygen act as chain carriers. The increased rates of decomposition and the reduced activation energy in the presence of the plasma could be explained on the basis of the observed large amount of atomic nitrogen which was probably formed as the result of reactions between excited atoms and ions of argon and the molecular nitrogen.
Resumo:
In this thesis we are concerned with finding representations of the algebra of SU(3) vector and axial-vector charge densities at infinite momentum (the "current algebra") to describe the mesons, idealizing the real continua of multiparticle states as a series of discrete resonances of zero width. Such representations would describe the masses and quantum numbers of the mesons, the shapes of their Regge trajectories, their electromagnetic and weak form factors, and (approximately, through the PCAC hypothesis) pion emission or absorption amplitudes.
We assume that the mesons have internal degrees of freedom equivalent to being made of two quarks (one an antiquark) and look for models in which the mass is SU(3)-independent and the current is a sum of contributions from the individual quarks. Requiring that the current algebra, as well as conditions of relativistic invariance, be satisfied turns out to be very restrictive, and, in fact, no model has been found which satisfies all requirements and gives a reasonable mass spectrum. We show that using more general mass and current operators but keeping the same internal degrees of freedom will not make the problem any more solvable. In particular, in order for any two-quark solution to exist it must be possible to solve the "factorized SU(2) problem," in which the currents are isospin currents and are carried by only one of the component quarks (as in the K meson and its excited states).
In the free-quark model the currents at infinite momentum are found using a manifestly covariant formalism and are shown to satisfy the current algebra, but the mass spectrum is unrealistic. We then consider a pair of quarks bound by a potential, finding the current as a power series in 1/m where m is the quark mass. Here it is found impossible to satisfy the algebra and relativistic invariance with the type of potential tried, because the current contributions from the two quarks do not commute with each other to order 1/m3. However, it may be possible to solve the factorized SU(2) problem with this model.
The factorized problem can be solved exactly in the case where all mesons have the same mass, using a covariant formulation in terms of an internal Lorentz group. For a more realistic, nondegenerate mass there is difficulty in covariantly solving even the factorized problem; one model is described which almost works but appears to require particles of spacelike 4-momentum, which seem unphysical.
Although the search for a completely satisfactory model has been unsuccessful, the techniques used here might eventually reveal a working model. There is also a possibility of satisfying a weaker form of the current algebra with existing models.
Resumo:
This thesis presents studies of the role of disorder in non-equilibrium quantum systems. The quantum states relevant to dynamics in these systems are very different from the ground state of the Hamiltonian. Two distinct systems are studied, (i) periodically driven Hamiltonians in two dimensions, and (ii) electrons in a one-dimensional lattice with power-law decaying hopping amplitudes. In the first system, the novel phases that are induced from the interplay of periodic driving, topology and disorder are studied. In the second system, the Anderson transition in all the eigenstates of the Hamiltonian are studied, as a function of the power-law exponent of the hopping amplitude.
In periodically driven systems the study focuses on the effect of disorder in the nature of the topology of the steady states. First, we investigate the robustness to disorder of Floquet topological insulators (FTIs) occurring in semiconductor quantum wells. Such FTIs are generated by resonantly driving a transition between the valence and conduction band. We show that when disorder is added, the topological nature of such FTIs persists as long as there is a gap at the resonant quasienergy. For strong enough disorder, this gap closes and all the states become localized as the system undergoes a transition to a trivial insulator.
Interestingly, the effects of disorder are not necessarily adverse, disorder can also induce a transition from a trivial to a topological system, thereby establishing a Floquet Topological Anderson Insulator (FTAI). Such a state would be a dynamical realization of the topological Anderson insulator. We identify the conditions on the driving field necessary for observing such a transition. We realize such a disorder induced topological Floquet spectrum in the driven honeycomb lattice and quantum well models.
Finally, we show that two-dimensional periodically driven quantum systems with spatial disorder admit a unique topological phase, which we call the anomalous Floquet-Anderson insulator (AFAI). The AFAI is characterized by a quasienergy spectrum featuring chiral edge modes coexisting with a fully localized bulk. Such a spectrum is impossible for a time-independent, local Hamiltonian. These unique characteristics of the AFAI give rise to a new topologically protected nonequilibrium transport phenomenon: quantized, yet nonadiabatic, charge pumping. We identify the topological invariants that distinguish the AFAI from a trivial, fully localized phase, and show that the two phases are separated by a phase transition.
The thesis also present the study of disordered systems using Wegner's Flow equations. The Flow Equation Method was proposed as a technique for studying excited states in an interacting system in one dimension. We apply this method to a one-dimensional tight binding problem with power-law decaying hoppings. This model presents a transition as a function of the exponent of the decay. It is shown that the the entire phase diagram, i.e. the delocalized, critical and localized phases in these systems can be studied using this technique. Based on this technique, we develop a strong-bond renormalization group that procedure where we solve the Flow Equations iteratively. This renormalization group approach provides a new framework to study the transition in this system.
Resumo:
Part I
Studies of vibrational relaxation in excited electronic states of simple diatomic molecules trapped in solid rare-gas matrices at low temperatures are reported. The relaxation is investigated by monitoring the emission intensity from vibrational levels of the excited electronic state to vibrational levels of the ground electronic state. The emission was in all cases excited by bombardment of the doped rare-gas solid with X-rays.
The diatomics studied and the band systems seen are: N2, Vegard-Kaplan and Second Positive systems; O2, Herzberg system; OH and OD, A 2Σ+ - X2IIi system. The latter has been investigated only in solid Ne, where both emission and absorption spectra were recorded; observed fine structure has been partly interpreted in terms of slightly perturbed rotational motion in the solid. For N2, OH, and OD emission occurred from v' > 0, establishing a vibrational relaxation time in the excited electronic state of the order, of longer than, the electronic radiative lifetime. The relative emission intensity and decay times for different v' progressions in the Vegard-Kaplan system are found to depend on the rare-gas host and the N2 concentration, but are independent of temperature in the range 1.7°K to 30°K.
Part II
Static crystal field effects on the absorption, fluorescence, and phosphorescence spectra of isotopically mixed benzene crystals were investigated. Evidence is presented which demonstrate that in the crystal the ground, lowest excited singlet, and lowest triplet states of the guest deviate from hexagonal symmetry. The deviation appears largest in the lowest triplet state and may be due to an intrinsic instability of the 3B1u state. High resolution absorption and phospho- rescence spectra are reported and analyzed in terms of site-splitting of degenerate vibrations and orientational effects. The guest phosphorescence lifetime for various benzene isotopes in C6D6 and sym-C6H3D3 hosts is presented and discussed.
Resumo:
In the preparation of small organic paramagnets, these structures may conceptually be divided into spin-containing units (SCs) and ferromagnetic coupling units (FCs). The synthesis and direct observation of a series of hydrocarbon tetraradicals designed to test the ferromagnetic coupling ability of m-phenylene, 1,3-cyclobutane, 1,3- cyclopentane, and 2,4-adamantane (a chair 1,3-cyclohexane) using Berson TMMs and cyclobutanediyls as SCs are described. While 1,3-cyclobutane and m-phenylene are good ferromagnetic coupling units under these conditions, the ferromagnetic coupling ability of 1,3-cyclopentane is poor, and 1,3-cyclohexane is apparently an antiferromagnetic coupling unit. In addition, this is the first report of ferromagnetic coupling between the spins of localized biradical SCs.
The poor coupling of 1,3-cyclopentane has enabled a study of the variable temperature behavior of a 1,3-cyclopentane FC-based tetraradical in its triplet state. Through fitting the observed data to the usual Boltzman statistics, we have been able to determine the separation of the ground quintet and excited triplet states. From this data, we have inferred the singlet-triplet gap in 1,3-cyclopentanediyl to be 900 cal/mol, in remarkable agreement with theoretical predictions of this number.
The ability to simulate EPR spectra has been crucial to the assignments made here. A powder EPR simulation package is described that uses the Zeeman and dipolar terms to calculate powder EPR spectra for triplet and quintet states.
Methods for characterizing paramagnetic samples by SQUID magnetometry have been developed, including robust routines for data fitting and analysis. A precursor to a potentially magnetic polymer was prepared by ring-opening metathesis polymerization (ROMP), and doped samples of this polymer were studied by magnetometry. While the present results are not positive, calculations have suggested modifications in this structure which should lead to the desired behavior.
Source listings for all computer programs are given in the appendix.
Resumo:
A new geometry-independent state - a traveling-wave wall state - is proposed as the mechanism whereby which the experimentally observed wall-localized states in rotating Rayleigh-Bénard convection systems preempt the bulk state at large rotation rates. Its properties are calculated for the illustrative case of free-slip top and bottom boundary conditions. At small rotation rates, this new wall state is found to disappear. A detailed study of the dynamics of the wall state and the bulk state in the transition region where this disappearance occurs is conducted using a Swift-Hohenberg model system. The Swift-Hohenberg model, with appropriate reflection-symmetry- breaking boundary conditions, is also shown to exhibit traveling-wave wall states, further demonstrating that traveling-wave wall states are a generic feature of nonequilibrium pattern-forming systems. A numerical code for the Swift-Hohenberg model in an annular geometry was written and used to investigate the dynamics of rotating Rayleigh-Bénard convection systems.
Resumo:
A series of experiments was conducted on the use of a device to passively generate vortex rings, henceforth a passive vortex generator (PVG). The device is intended as a means of propulsion for underwater vehicles, as the use of vortex rings has been shown to decrease the fuel consumption of a vehicle by up to 40% Ruiz (2010).
The PVG was constructed out of a collapsible tube encased in a rigid, airtight box. By adjusting the pressure within the airtight box while fluid was flowing through the tube, it was possible to create a pulsed jet with vortex rings via self-excited oscillations of the collapsible tube.
A study of PVG integration into an existing autonomous underwater vehicle (AUV) system was conducted. A small AUV was used to retrofit a PVG with limited alterations to the original vehicle. The PVG-integrated AUV was used for self-propelled testing to measure the hydrodynamic (Froude) efficiency of the system. The results show that the PVG-integrated AUV had a 22% increase in the Froude efficiency using a pulsed jet over a steady jet. The maximum increase in the Froude efficiency was realized when the formation time of the pulsed jet, a nondimensional time to characterize vortex ring formation, was coincident with vortex ring pinch-off. This is consistent with previous studies that indicate that the maximization of efficiency for a pulsed jet vehicle is realized when the formation of vortex rings maximizes the vortex ring energy and size.
The other study was a parameter study of the physical dimensions of a PVG. This study was conducted to determine the effect of the tube diameter and length on the oscillation characteristics such as the frequency. By changing the tube diameter and length by factors of 3, the frequency of self-excited oscillations was found to scale as f~D_0^{-1/2} L_0^0, where D_0 is the tube diameter and L_0 the tube length. The mechanism of operation is suggested to rely on traveling waves between the tube throat and the end of the tube. A model based on this mechanism yields oscillation frequencies that are within the range observed by the experiment.