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UNT Scholarly Works
- An Abstract Index Theorem on Non-Compact Riemannian Manifolds
- This article discusses an abstract index theorem on non-compact Riemannian manifolds. Abstract: We prove an abstract index theorem for essentially self-adjoint Fredholm supersymmetric first-order elliptic differential operators on Hermitian vector bundles over complete oriented Riemannian manifolds. According to our main result the supersymmetric L2-index of such an operator can be expressed as the sum of a "local contribution" (the familiar Atiyah-Singer index form, suitably restricted to and integrated over a finite region) and a "boundary contribution" (which depends only on the restriction of the operator at large distances). This is done by splicing together local parametrices and Green's operators defined "at infinity". The result yields (in fact is equivalent to) a generalisation of the relative index theorem of Gromov and Lawson. digital.library.unt.edu/ark:/67531/metadc159527/
- Anomalous diffusion and ballistic peaks: A quantum perspective
- This article discusses anomalous diffusion and ballistic peaks. Abstract: The quantum kicked rotor and the classical kicked rotor are both shown to have truncated Lévy distributions in momentum space, when the classical phase space has accelerator modes embedded in a chaotic sea. The survival probability for classical particles at the interface of an accelerator mode and the chaotic sea has an inverse power-law structure, whereas that for quantum particles has a periodically modulated inverse power law, with the period of oscillation being dependent on Planck's constant. These logarithmic oscillations are a renormalization group property that disappears as ħ → 0 in agreement with the correspondence principle. digital.library.unt.edu/ark:/67531/metadc75417/
- Anomalous diffusion and environment-induced quantum decoherence
- This article discusses anomalous diffusion and environment-induced quantum decoherence. Abstract: We study the anomalous diffusion resulting from the standard map in the so-called accelerating state, and we observe that it is determined by unusually large times of sojourn of the classical trajectories in the fractal region at the border between the chaotic sea and the acceleration island. The quantum-mechanical breakdown of this property implies a coherence among so slightly different values of momentum as to become much more robust against environment fluctuations than the quantum localization corresponding to normal diffusion. digital.library.unt.edu/ark:/67531/metadc139477/
- Are Net Discount Rates Stationary?: Some Further Evidence
- This article discusses net discount rates. Abstract: Gamber and Sorensen provide evidence suggesting that the net discount ratio experienced a level shift in the mean between 1977 and 1981. If such a shift occurred, the nonlinearity in the data shows up as a failure to reject the null hypothesis that a unit root is present; that is, the series is I(1). In this reply, evidence is presented - the Phillips-Perron test and a univariate version of the Stock-Watson q-test - suggesting that the net discount ratio is stationary. Hence, the mean is constant. In addition, if one extends the analysis to include the 1989 through 1993 period, the net discount ratio appears to be reverting. digital.library.unt.edu/ark:/67531/metadc71791/
- Are Net Discount Ratios Stationary?: The Implications For Present Value Calculations
- Abstract: This article analyzes the relationship between real interest rates and real growth rates in wages. The stationary of these time series has been discussed in the literature. However, since the net discount ratio, (1 + gτ)/(1 + rτ), is a nonlinear transformation, it is not necessarily stationary even if the interest rate and growth rate in wages series are each stationary. On the other hand, the net discount ratio may be stationary even if the interest rate and growth rate series are both non-stationary. The significant finding of this article is that this ratio is stationary. This conclusion appears robust since it holds for at least four different Treasury securities analyzed: three month, six month, one year, and three year. Therefore, a real net discount ratio, (1 + gτ)/(1 + rτ), can be used with confidence in constructing present value forecasts of expected earnings. digital.library.unt.edu/ark:/67531/metadc71790/
- Atomic resolution ultrahigh vacuum scanning tunneling microscopy of epitaxial diamond (100) films
- In this article, the authors report atomic resolution images of chemical vapor deposition grown epitaxial diamond (100) films obtained in ultrahigh vacuum (UHV) with a scanning tunneling microscope. A (2X1) dimer surface reconstruction and amorphous atomic regions are observed. The (2X1) unit cell is measured to be 0.51±0.01X0.25±0.01 nm2. The amorphous regions are identified as carbon. A radial structure 1.5 nm in diameter is observed on a plane at a 20° slope to the (2X1) surface. Tunneling current versus voltage spectra in UHV and Raman spectra are also obtained. digital.library.unt.edu/ark:/67531/metadc84147/
- Bianucci, Mannella, and Grigolini Reply
- This article is a reply to a comment by Massimo Falcioni and Angelo Vulpiani. In a previous letter, the authors have discussed the linear response theory (LRT) and shown that the breakdown of this theory occurring at intermediate times, observed in an earlier paper [2] as well as in [1], disappears upon an increase of the number of degrees of freedom. In a comment to [1] Falcioni and Vulpiani [3] claim that this breakdown is rather a consequence of the lack of mixing: according to them, regardless of the number of degrees of freedom, mixing is the key ingredient behind the LRT. digital.library.unt.edu/ark:/67531/metadc77166/
- Calculation of a Methane C-H Oxidative Addition Trajectory: Comparison to Experiment and Methane Activation by High-Valent Complexes
- This article discusses the calculation of a methane C-H oxidative addition trajectory. Abstract: An effective core potential (ECP), parallel supercomputing study of methane activation by 14-electron, Ir(PH₃)₂(X) complexes (X = H, Cl) is presented. Considerable weakening of the coordinated methane C-H bond occurs upon formation of an ɳ²-CH coordinated (X)(PH₃)₂Ir•••HCH₃ adduct. A more strongly bound adduct (with greater weakening of the coordinated C-H bond) occurs when X = Cl versus X = H. The calculated Ir(PH₃)₂(H) + CH₄ → Ir(PH₃)₂(H)₂(Me) reaction enthalpy is -12.8 kcal mol⁻¹, and -41.6 kcal mol⁻¹ for the chloro analogue. The intrinsic reaction coordinate is calculated and compared to an experimental trajectory. Analysis of the wave function along the intrinsic reaction coordinate (IRC) suggests that although donation of electron density from methane to metal is essential for adduct formation, it is not until backdonation to σ* сʜ increases that the C-H bond is activated and cleaved. The electronic and molecular structure of the reacting system along the IRC suggest a two-stage mechanism: substrate to complex donation is important in the early part of the reaction (electrophilic stage) while complex to substrate backdonation is necessary later on (nucleophilic stage) for C-H scission. Finally, comparison of IRCs for low- and high-valent methane-activating complexes shows similar topology in the early portion of the activation event; differentiation between oxidative addition and σ-bond metathesis occurs at the point at which there is a shift from the electrophilic to nucleophilic stage of the reaction. digital.library.unt.edu/ark:/67531/metadc107777/
- Chaos and thermal conductivity
- This article discusses chaos and thermal conductivity. Abstract: We argue that the condition of local thermal equilibrium realized several years ago by Rich and Visscher [Phys. Rev. B 11, 2164 (1975)] through a process of mathematical convergence can be obtained dynamically by adopting the prescription of a recent paper [M. Bianucci, R. Mannella, B.J. West, and P. Grigolini, Phys. Rev. E 51, 3002 (1995)]. This should contribute to shedding light on the still unsolved problem fo the microscopic derivation of the heat Fourier law. digital.library.unt.edu/ark:/67531/metadc139502/
- Charge-state dependence of K-shell x-ray production in aluminum by 2-12-MeV carbon ions
- This article discusses charge-state dependence of K-shell x-ray production in aluminum by 2-12-MeV carbon ions. Abstract: Charge-state dependence for K-shell x-ray production cross sections in 13Al bombarded by 2-12-MeV 6C ions with charge states from 2+ to 6+ was measured using a Si(Li) detector. A thin Al target was used to ensure single collision conditions. Contributions of the electron capture as well as direct ionization to the inner-shell ionization were determined by an analysis of the charge-state dependence of the target x-ray production. The measurements are compared with the prediction of the ECPSSR theory using a single-hole fluorescence yield. The ECPSSR theory is based on the perturbed stationary state (PSS) formalism and relativistic efforts (R) for the target electrons, and energy loss (E) and Coulomb deflection (C) of the projectile. In general, this theory gives reasonable agreement with the data for carbon ions without K vacancies while it overpredicts the data for carbon ions with K vacancies. The significant underprediction of the data at the lowest energy is likely associated with the molecular-orbital effect that is not accounted for in the ECPSSR theory. digital.library.unt.edu/ark:/67531/metadc139497/
- Charge-state dependence of M-shell x-ray production in 67Ho by 2-12-MeV carbon ions
- This article discusses charge-state dependence of M-shell x-ray production in 67Ho by 2-12-MeV carbon ions. Abstract: Charge-state dependence of M-shell x-ray production cross sections of 67Ho bombarded by 2-12-MeV carbon ions, with and without K-shell vacancies, were measured using a windowless Si(Li) x-ray detector with a full-width-at-half-maximum resolution of 135 eV at 5.9 keV. Carbon ions of different charge states were produced using a postacceleration, nitrogen gas stripping cell. The carbon ions were then magnetically analyzed to select the desired charge state and energy before entering the target chamber. The total M-shell and Mζ, Mα,β, and Mγ x-ray cross sections were measured. The electron-capture (EC) contributions as well as the direct-ionization (DI) contributions can be determined by making a comprehensive study of the projectile-charge-state dependence of the target x-ray production cross sections for targets in which the single-collision realm is maintained. In this paper, both EC and DI contributions and the total M-shell x-ray production cross sections are compared to both the first Born theory and to the perturbed-stationary-state theory with energy-loss, Coulomb-deflection, and relativistic corrections. digital.library.unt.edu/ark:/67531/metadc139496/
- Comments on the Competitive Preferential Solvation Theory
- This article offers comments on the competitive preferential solvation theory. Abstract: Simple additive relationships for the physico-chemical properties of a solute dissolved in binary solvent mixtures are developed from the competitive preferential solvation model. Additive expressions for solute mole fraction solubility and logarithm of solute solubility are mathematically identical to equations derived previously from the microscopic partition and basic nearly ideal binary solvent models. Calculated values based on the various additive relationships are compared to carbazole solubilities in ten binary solvent mixtures containing dibutyl ether with n-hexane, n-heptane, n-octane, cyclohexane, cyclo-octane, methylcyclohexane, iso-octane, n-hexadecane, squalane and t-butylcyclohexane. digital.library.unt.edu/ark:/67531/metadc157300/
- Control of chaos in a CO2 laser
- This article discusses the control of chaos in a CO2 laser. Abstract: We report the experimental control of chaos in an optically modulated CO2 laser. The CO2 laser was driven into chaos by injecting a feedback beam modulated by an electro-optical modulator. Control of chaos was achieved using a modified proportional feedback technique in which the control pulses were delayed by approximately one relaxation period. Using this technique, it was possible to control unstable periodic orbits up to period 6. digital.library.unt.edu/ark:/67531/metadc84149/
- Design of highly specific cytotoxins by using trans-splicing ribozymes
- This article discusses the design of highly specific cytotoxins by using trans-splicing ribozymes. Abstract: We have designed ribozymes based on a self-splicing group I intron that can trans-splice exon sequences into a chosen RNA target to create a functional chimeric mRNA and provide a highly specific trigger for gene expression. We have targeted ribozymes against the coat protein mRNA of a widespread plant pathogen, cucumber mosaic virus. The ribozymes were designed to trans-splice the coding sequence of the diphtheria toxin A chain in frame with the viral initiation codon of the target sequence. Diphtheria toxin A chain catalyzes the ADP ribosylation of elongation factor 2 and can cause the cessation of protein translation. In a Saccharomyces cerevisiae model system, ribozyme expression was shown to specifically inhibit the growth of cells expressing the virus mRNA. A point mutation at the target splice site alleviated this ribozyme-mediated toxicity. Increasing the extent of base pairing between the ribozyme and target dramatically increased specific expression of the cytotoxin and reduced illegitimate toxicity in vivo. Trans-splicing ribozymes may provide a new class of agents for engineering virus resistance and therapeutic cytotoxins. digital.library.unt.edu/ark:/67531/metadc83320/
- Direct evidence for the amorphous silicon phase in visible photoluminescent porous silicon
- This article discusses direct evidence for the amorphous silicon phase in visible photoluminescent porous silicon. Abstract: We report on micro-Raman spectroscopy studies of porous silicon which show an amorphous silicon Raman line at 480 R cm-1 from regions that emit visible photoluminescence. A Raman line corresponding to microcrystalline silicon at 510 R cm-1 is also observed. X-ray photoelectron spectroscopy data is presented which shows a high silicon-dioxide content in porous silicon consistent with an amorphous silicon phase. digital.library.unt.edu/ark:/67531/metadc84327/
- Dynamic Approach to the Thermodynamics of Superdiffusion
- This article discusses dynamic approach to the thermodynamics of superdiffusion. Abstract: We address the problem of relating thermodynamics to mechanics in the case of microscopic dynamics without a finite time scale. The solution is obtained by expressing the Tsallis entropic index q as a function of the Lévy index α, and using dynamic rather than probabilistic arguments. digital.library.unt.edu/ark:/67531/metadc77167/
- Dynamical approach to Lévy processes
- This article discusses a dynamical approach to Lévy processes.Abstract: We derive the diffusion process generated by a correlated dichotomous fluctuating variable y starting from a Liouville-like equation by means of a projection procedure. This approach makes it possible to derive all statistical properties of the diffusion process from the correlation function of the dichotomous fluctuating variable Φy(t). Of special interest is that the distribution of the times of sojourn in the two states of the fluctuating process is proportional to d²Φy(t)/dt². Furthermore, in the special case where Φy(t) has an inverse power law, with the index β ranging from 0 to 1, thus making it nonintegrable, the authors show analytically that the statistics of the diffusing variable approximate in the long-time limit the α-stable Lévy distributions. The departure of the diffusion process of dynamical origin from the ideal condition of the Lévy statistics is established by means of a simple analytical expression. We note, first of all, that the characteristic function of a genuine Lévy process should be an exponential in time. We evaluate the correction to this exponential and show it to be expressed by a harmonic time oscillation modulated by the correlation function Φy(t). Since the characteristic function can be given a spectroscopic significance, we also discuss the relevance of the results within this context. digital.library.unt.edu/ark:/67531/metadc139498/
- Dynamical model for DNA sequences
- This article discusses a dynamical model for DNA sequences. Abstract: We address the problem of DNA sequences, developing a "dynamical" method based on the assumption that the statistical properties of DNA paths are determined by the joint action of two processes, one deterministic with long-range correlations and the other random and δ-function correlated. The generator of the deterministic evolution is a nonlinear map belonging to a class of maps recently tailored to mimic the processes of weak chaos responsible for the birth of anomalous diffusion. It is assumed that the deterministic process corresponds to unknown biological rules that determine the DNA path, whereas the noise mimics the influence of an infinite-dimensional environment on the biological process under study. We prove that the resulting diffusion process, if the effect of the random process is determined by the joint action of the deterministic and the random process, the correlation effects of the "deterministic dynamics" are canceled on the short-range scale, but show up in the long-range one. We denote their prescription to generate statistical sequences as the copying mistake map (CMM). We carry out their analysis of several DNA sequences and their CMM realizations with a variety of techniques and the authors especially focus on a method of regression to equilibrium, which they call the Onsager analysis. With these techniques the authors establish the statistical equivalence of the real DNA sequences with their CMM realizations. We show that long-range correlations are present in exons as well as in introns, but are difficult to detect, since the exon "dynamics" is shown to be determined by the entanglement of three distinct and independent CMM's. digital.library.unt.edu/ark:/67531/metadc139499/
- An Effective Core Potential Study of Transition-Metal Chalcogenides. 1. Molecular Structure
- This article discusses an effective core potential study of transition-metal chalcogenides. Abstract: A structural analysis is reported of roughly 150 transition-metal (TM)-chalcogenido complexes in a variety of chemical environments. With few exceptions, agreement between calculated and experimental geometries is excellent. The research provides convincing evidence that computational methods employed are adequately describing the bonding in these diverse TM complexes. Interesting trends in relative TMCh (Rмсh-Rмсh) bond lengths are found. Experimental and computational data show that other than the zirconocene-and halfnocene-oxos there is similar behavior in relative bond lengths for widely varying TM-chalcogenido complexes. Relative bond lengths versus oxo (S-O, Se-O, and Te-O) in group IVB metallocenes tend to be larger than for other families of complexes and show less variation among the heavier chalcogens (Se-S, Te-S, and Te-Se). Analysis of localized wave functions for Cp₂ZrCh point to a greater contribution from a singly-bonded Zr-Ch structure (relative to Zr=Ch) when Ch is O compared to heavier chalcogens. Taken together, the data suggest that there is a fundamental difference in the Zr-oxo (and Hf-oxo) bond in relation to heavier chalcogens, consistent with recent experimental data. In previous studies of multiply bonded TM complexes the authors have focused on the ability of ECPs to make computations feasible for complexes incorporating even the heaviest transition metals. The present work also evaluates ECP methods for heavier main group (MG) elements. The chalcogens (CH) O, S, Se, and Te are included in this study. digital.library.unt.edu/ark:/67531/metadc107778/
- Effects of O2, H2, and N2 gases on the field emission properties of diamond-coated microtips
- This article discusses the effects of O2, H2, and N2 gases on the field emission properties of diamond-coated microtips. Abstract: We report the effects of O2, H2, and N2 residual gases on the field emission properties of uncoated and diamond-coated individual Mo microtips. The microtips are made using electrochemical etching techniques and positioned 5 µm from the anode using a scanning tunneling microscopy system. The authors observe that the field emission (FE) current and turn-on voltage of diamond-coated microtips are significantly less degraded by O2 exposure that those of uncoated Mo microtips. H2 exposure enhances the FE properties of both uncoated and diamond-coated microtips, while N2 exposure does not have any significant effect. digital.library.unt.edu/ark:/67531/metadc84151/
- Estimating Solid-Liquid Phase Change Enthalpies and Entropies
- This article discusses estimating solid-liquid phase change enthalpies and entropies. Abstract: A group additivity method based on molecular structure is described that can be used to estimate solid-liquid total phase change entropy (∆₀ᵀ(fus)S(tpce)) and enthalpy (∆₀ᵀ(fus)H(tpce)) of organic molecules. The estimation of these phase changes is described and numerous examples are provided to guide the user in evaluating these properties for a broad range of organic structures. A total of 1858 compounds were used in deriving the group values and these values are tested on a database of 260 additional compounds. The absolute average and relative errors between experimental and calculated values for these 1858 compounds are 9.9 J-mol⁻¹·K⁻¹ and 3.52 kJ·mol⁻¹, and 0.154 and 0.17 for ∆₀ᵀ(fus)S(tpce) and ∆₀ᵀ(fus)H(tpce), respectively. For the 260 test compounds, standard deviations of ± 13.0 J·mol⁻¹·K⁻¹ (∆₀ᵀ(fus)S(tpce)) and ±4.88 kJ mol⁻¹ (∆₀ᵀ(fus)H(tpce)) between experimental and calculated values were obtained. Estimations are provided for both databases. Fusion enthalpies for some additional compounds not included in the statistics are also included in the tabulation. digital.library.unt.edu/ark:/67531/metadc152463/
- Experimental evidence for a discrete transition to channeling for 1.0-MeV protons in Si〈100〉
- This article discusses experimental evidence for a discrete transition to channeling for 1.0-MeV protons in Si〈100〉. Abstract: The present work reports the experimental evidence of anomalies exhibited by the energy loss and energy straggling of channeled protons in silicon in transmission measurements versus the incident angle. Results are presented for 1.0-MeV protons channeled along the 〈100〉 axis for a silicon foil of 3.8 μm thickness. It is shown that the transition from random to a channeling condition is discrete. The energy spectra of transmitted ions show a random peak (lower energy) and a channeled peak (higher energy). The random peak has a fixed energy, while the energy of the channeled peak increases as the target crystal's axis approaches alignment with the direction of the incident ion beam. The results support a model suggesting that the channeled ions lose energy only to valence electrons and are concentrated in a narrow cone about the direction of incidence when they emerge from the crystal. The energy straggling of channeled particles reaches a minimum in the hyper-channeled condition. Both the energy loss and the energy straggling of channeled protons show a dependence on the local electron density. digital.library.unt.edu/ark:/67531/metadc139489/
- Fabrication of silicon-based optical components for an ultraclean accelerator mass spectronomy negative ion source
- This article discusses fabrication of silicon-based optical components for an ultraclean accelerator mass spectronomy negative ion source. Abstract: An ultraclean accelerator mass spectronomy negative ion source for semiconductor material mass analysis has been built and is in operation at the University of North Texas' Ion Beam Modification and Analysis Laboratory (IBMAL). The source is unique in that the active surfaces and apertures of the optical components in the ion source have been fabricated from high-purity single crystal silicon. This prevents both the 133Cs+ beam incident on the semiconductor samples and the negative ions from the sample surfaces from "seeing" and sputtering any metal surfaces (mostly stainless steel) in the beamline. The Cs+ beam can be rastered across the sample surface and the impact energy is adjustable to control depth-profiling rates. An ultraclean ion source of this type is necessary to prevent the injection of Fe and other beamline elements onto the sample or into the tandem accelerator, which is equivalent to putting an impurity signal into the mass analysis of the semiconductor sample. Suppression of these elements increases the sensitivity of the analysis to one part in 10¹² for many masses. The fabrication and alignment of the optical components-einzel lenses, steerers, raster/scanners, and Faraday cups-in the negative ion source will be presented. Also, simulation trajectories are presented to show (1) the interaction of the incident Cs+ ion beam, the semiconductor sample, and holder (biased up to -30 kV), the extracted beam in the sample chamber, and associated potential field lines; and (2) the potential field lines of the octupole steerers. digital.library.unt.edu/ark:/67531/metadc146573/
- Fractional Brownian motion as a nonstationary process: An alternative paradigm for DNA sequences
- This article discusses fractional Brownian motion as a nonstationary process. Abstract: The long-range correlations in DNA sequences are currently interpreted as an example of stationary fractional Brownian motion (FBM). First the authors show that the dynamics of a dichotomous stationary process with long-range correlations such as that used to model DNA sequences should correspond to Lévy statistics and not to FBM. To explain why, in spite of this, the statistical analysis of the data seems to be compatible with FBM, the authors notice that an initial Gaussian condition, generated by a process foreign to the mechanism establishing the long-range correlations and consequently implying a departure from the stationary condition is maintained approximately unchanged for very long times. This is so because due to the nature itself of the long-range correlation process, it takes virtually an infinite time for the system to reach the genuine stationary state. Then the authors discuss a possible generator of initial Gaussian conditions, based on a folding mechanism of the nucleic acid in the cell nucleus. The model adopted is compatible with the known biological and physical constraints, namely, it is shown to be consistent with the information of current biological literature on folding as well as with the statistical analyses of DNA sequences. digital.library.unt.edu/ark:/67531/metadc75416/
- Fractional calculus as a macroscopic manifestation of randomness
- This article discusses fractional calculus as a macroscopic manifestation of randomness. Abstract: We generalize the method of Van Hove [Physica (Amsterdam) 21, 517 (1955)] so as to deal with the case of nonordinary statistical mechanics, that being phenomena with no time-scale separation. We show that in the case of ordinary statistical mechanics, even if the adoption of the Van Hove method imposes randomness upon Hamiltonian dynamics, the resulting statistical process is described using normal calculus techniques. On the other hand, in the case where there is no time-scale separation, this generalized version of Van Hove's method not only imposes randomness upon the microscopic dynamics, but it also transmits randomness to the macroscopic level. As a result, the correct description of macroscopic dynamics has to be expressed in terms of the fractional calculus. digital.library.unt.edu/ark:/67531/metadc77121/
- High-Valent Transition-Metal Alkylidene Complexes: Effect of Ligand and Substituent Modification
- This article discusses high-valent transition-metal alkylidene complexes. Abstract: An ab initio investigation into the effects of ligand and substituent modification on the metal-carbon double bond is reported. Prototypical group IVB (Ti, Zr, Hf) and Group VB (Nb, Ta) alkylidenes are chosen for this study. The MC/LMO/CI (multiconfiguration/localized molecular orbital/configuration interaction) procedure is used to examine the electronic structures of these complexes in terms of the prime resonance contributors to the ground-state wave function. The main conclusion drawn from this work is that the intrinsic nature of the metal-carbon double bond can typically be changed only within certain limits by modification of the electronegativity of the ligands (L) and substituents (Z). In other words, the Ta=C bond in H₃TaCCl₂ and Cl₃TaCH₂ and presumably in experimentally characterized analogues with larger ligands and substituents, e.g., Cp and neopentyl. Significant changes in the electronic structure are effected in three ways: The first way is through the introduction of a highly electropositive substituent, e.g., Li. This makes the metal-carbon bond closer to a triple bond for the Ta-alkylidenes. The second way to change the electronic structure of the alkylidenes significantly is to change the central metal atom. The heaviest members of groups IVB (Hf) and VB (Ta) are the most nucleophilic at the α-carbon. The third way in which the metal-carbon bond could be significantly altered is through the use of π-donor substituents. The introduction of π-donor substituents on Cα increases the electrophilicity of the α-carbon. digital.library.unt.edu/ark:/67531/metadc107774/
- Historic Archaeology of the Johnson and Jones Farmsteads in the Ray Roberts Lake Area: 1850-1950
- This study represents the findings of research done on the Jones and Johnson farms, "situated in Johnson Branch Park in the north-central portion of the Ray Roberts Lake area." The purpose of the study was to offset future disturbances and damages to these farmsteads, and it includes "archival investigations, architectural documentation, oral-history interviews of long-time area residents and family members, farm equipment and artifact analyses, archaeological excavations, stabilization measures, and the development of interpretative exhibits for area schools, museums, and the general public" (p. i). digital.library.unt.edu/ark:/67531/metadc29393/
- K-shell x-ray-production cross sections in 6C, 8O, 9F, 11Na, 12Mg, and 13Al, by 0.75- to 4.5-MeV protons
- This article discusses K-shell x-ray-production cross sections. Abstract: K-shell x-ray-production cross sections are reported for elements with K-shell x-ray energies between 277 eV (C) and 1487 eV (Al). The x-ray measurements were made with a windowless Si(Li) detector that was calibrated for efficiency by comparing bremsstrahlung spectra from electron bombardment of thin foils of aluminum, silver, and gold with theoretically determined bremsstrahlung spectral distributions. The x-ray-production cross-section measurements are compared to first-order Born and perturbed-stationary-state with energy-loss, Coulomb deflection, and relativistic corrections (ECPSSR) ionization theories using single-hole fluorescence yields. The ECPSSR and first-order Born theoretical predictions are, in general, in close agreement with each other and both generally fit the data quite well. digital.library.unt.edu/ark:/67531/metadc139500/
- Lévy diffusion as an effect of sporadic randomness
- This article discusses Lévy diffusion as an effect of sporadic randomness. Abstract: The Lévy diffusion processes are a form of nonordinary statistical mechanics resting, however, on the conventional Markov property. As a consequence of this, their dynamic derivation is possible provided that (i) a source of randomness is present in the corresponding microscopic dynamics and (ii) the consequent process of memory erasure is properly taken into account by the theoretical treatment. digital.library.unt.edu/ark:/67531/metadc77160/
- Linear Response of Hamiltonian Chaotic Systems as a Function of the Number of Degrees of Freedom
- This article discusses the linear response of Hamiltonian chaotic systems as a function of the number of degrees of freedom. Using numerical simulations the authors show that the response to weak perturbations of a variable of Hamiltonian chaotic systems depend on the number of degrees of freedom: When this is small (≈2) the response is not linear, in agreement with the well known objections to the Kubo linear response theory, while, for a larger number of degrees of freedom, the response becomes linear. This is due to the fact that increasing the number of degrees of freedom the shape of the distribution function, projected onto the subspace of the variable of interest, becomes fairly "regular." digital.library.unt.edu/ark:/67531/metadc139479/
- Low-level copper concentration measurements in silicon wafers using trace-element accelerator mass spectrometry
- This article discusses low-level copper concentration measurements in silicon wafers using trace-element accelerator mass spectrometry. Accelerator mass spectrometry (AMS) is now widely used in over 30 laboratories throughout the world to measure ratios of the abundances of long-lived radioisotopes such as ¹⁰Be, ¹⁴C, ³⁶Cl, and ¹²⁷I to their stable isotopes at levels as low as 10(-16). Trace-element AMS (TEAMS) is an application of AMS to the measurement of very low levels of stable isotope impurities. Copper concentrations as low as 1 part per billion have been measured in silicon wafers. In this letter, the authors demonstrate the use of TEAMS to measure previously unknown copper concentration depth profiles in As-implanted Si wafers at a few parts per billion. To verify the TEAMS technique, the samples from the same wafer were measured with secondary ion mass spectrometry, which showed the same profiles, albeit plateauing out at a concentration level six times higher than the TEAMS measurement. The ability to measure at these levels is especially significant in light of the recent moves towards the use of copper interconnects in place of aluminum in integrated circuits. digital.library.unt.edu/ark:/67531/metadc146577/
- The Markov approximation revisited: inconsistency of the standard quantum Brownian motion model
- In this article, the authors revisit the Markov approximation necessary to derive ordinary Brownian motion from a model widely adopted in literature for this specific purpose. The authors show that this leads to internal inconsistencies, thereby implying that further search for a more satisfactory model is required. digital.library.unt.edu/ark:/67531/metadc139465/
- Methane Activation by Group IVB Imido Complexes
- This article discusses methane activation by group IVB imido complexes. An ab initio study of methane activation by group IVB imido complexes, when coupled with available experimental data, reveals an interesting picture of this important reaction. Initial interaction of methane and (H)₂M=NH leads to the formation of alkane complexes bound by ≈9 kcal mol⁻¹. Experiment indicates that the polarity of the metal-ligand bond upon which the C-H is activated plays an important role in facilitating subsequent scission. Calculations support this hypothesis and suggest that formation of the alkane complex acts to increase Cδ-Hδ polarization, setting the stage for C-H cleavage. Calculated methane elimination barriers for (H)₂M(CH₃)(NH₂) (M=Ti, Zr, Hf) are in good agreement with experimental models in terms of absolute numbers and trends as a function of metal. Calculated methane activation barriers follow the order Ti > Zr > Hf, in line with calculated exothermicities. Calculated geometries indicate a late transition state for methane elimination, in agreement with experimentally determined activation parameters. The TSs have a kite-shaped geometry with an obtuse angle about the H of the C-H bond being activated (Ht) and a short MHt distance, 1-2% greater than normal. The short MHt distance suggests a stabilizing interaction, supported by a positive bond overlap population. Calculation of the intrinsic reaction coordinate demonstrates the importance of agostic interactions between N-H and M along the reaction coordinate. digital.library.unt.edu/ark:/67531/metadc107807/
- Modeling Nonlinear Optical Properties of Transition Metal Complexes. Basis Set, Effective Core Potential, and Geometry Effects
- This article discusses modeling nonlinear optical properties of transition metal complexes. Nonlinear optical (NLO) properties of transition metal complexes are studied using quantum chemical calculations. By comparison with all electron calculations, effective core potentials have been shown to be competent for the calculation of NLO properties as long as the valence basis sets are comparable. While overall the basis set effects are important for calculation of NLO properties, they are found to be less important for the central transition metal than for the surrounding ligands. Augmenting the basis set of main group elements with diffuse, s, p, and d functions in a proper way could provide the best compromise between speed and accuracy of the computation. Interesting trends are found in the calculation of NLO properties of [MO₄]q⁻. Both polarizability (α) and second hyperpolarizability (y) decrease toward the right across the transition series. The second series [MO₄]q⁻ have the largest α among the three metalates in a triad. For group IVB and VB complexes with larger charges (-4 and -3, respectively), the second series [MO₄]q⁻ have the largest y, while for groups VIB, VIIB, and VIII, with less anionic metalates (-2, -1, and 0, respectively), the third series metalates have the largest y. The relative difference in both α and y values among the three series in the same group is much smaller than between different groups. Overall, variations in the calculated values of NLO properties correlate with M-O bond lengths and hence the size of the metalate ion. digital.library.unt.edu/ark:/67531/metadc107805/
- Molecular Modeling of Vanadium-Oxo Complexes. A Comparison of Quantum and Classical Methods
- This article discusses molecular modeling of vanadium-oxo complexes. A force field for vanadium-oxos was developed and tested with a variety of complexes with coordination numbers of 5 or 6 and formal oxidations states of +4 or +5 on the metal. Similarly, a semiempirical quantum mechanical method for transition metals was extended to vanadium. In this research soft and hard ligands were studied, as were ligands coordinated through single, multiple, and dative bonds. Despite the diversity of vanadium coordination chemistry, generally good modeling is achieved in a fraction of the time with less computational resources using molecular mechanics and semiempirical quantum mechanics. The L₄V⁴⁺O and L₅V⁵⁺O groups were emphasized given their prevalence and importance. In general, the predictive ability was superior for the former structural motif. The combination of molecular mechanics and semiempirical quantum calculations provide an effective and efficient tool for analysis of the steric and electronic energy differences between isomers. digital.library.unt.edu/ark:/67531/metadc107804/
- Noise-induced transition from anomalous to ordinary diffusion: The crossover time as a function of noise intensity
- In this article, the authors study the interplay between a deterministic process of weak chaos, responsible for the anomalous diffusion of a variable x, and a white noise of intensity ≡. The deterministic process of anomalous diffusion results from the correlated fluctuations of a statistical variable ξ between two distinct values +1 and -1, each of them characterized by the same waiting time distribution ψ(t), given by ψ(t)≃ t(-μ) with 2 < μ < 3, in the long-time limit. The authors prove that under the influence of a weak white noise of intensity ≡, the process of anomalous diffusion becomes normal at a time t(c) given by t(c) ~ 1/≡(β)(μ). Here β(μ) is a function of μ which depends on the dynamical generator of the waiting-time distribution ψ(t). The authors derive an explicit expression for β(μ) in the case of two dynamical systems, a one-dimensional superdiffusive map and the standard map in the accelerating state. The theoretical prediction is supported by numerical calculations. digital.library.unt.edu/ark:/67531/metadc139501/
- Non-Gaussian statistics of anomalous diffusion: The DNA sequences of prokaryotes
- This article discusses non-Gaussian statistics of anomalous diffusion. The authors adopt a non-Gaussian indicator to measure the deviation from Gaussian statistics of a diffusion process generated by dichotomous fluctuations with infinite memory. The authors also make analytical predictions on the transient behavior of the non-Gaussian indicator as well as on its stationary value. The authors then apply this non-Gaussian analysis to the DNA sequences of prokaryotes adopting a theoretical model where the "DNA dynamics" are assumed to be determined by the statistical superposition of two independent generators of fluctuations: a generator of fluctuations with no correlation and a generator of fluctuations with infinite correlation "time". The authors study also the influence that the finite length of the observed sequences has on the short-range fluctuation and sequence truncation. Nevertheless, under proper conditions, fulfilled by all the DNA sequences of prokaryotes that have been examined, a non-Gaussian signature remains to signal the correlated nature of the driving process. digital.library.unt.edu/ark:/67531/metadc75418/
- The observation of silicon nanocrystals in siloxene
- In this article, the authors report the direct observation of silicon nanocrystals in unannealed siloxene using high resolution transmission electron microscopy. The microstructure consists of an amorphous matrix plus silicon crystallites with dimensions of a few nanometers. This is additional evidence that the photoluminescence of silicon-based materials is due to quantum confinement. digital.library.unt.edu/ark:/67531/metadc84364/
- Principal Resonance Contributors to High-Valent, Transition-Metal Alkylidene Complexes
- This article discusses principal resonance contributors to high-valent, transition-metal alkylidene complexes. The results of ab initio calculations are reported for prototypical high-valent, alkylidene complexes. Stationary points on each potential energy surface are characterized and compared to experimental information where available; as long as a suitably flexible valence basis set is used, good agreement between theoretically calculated and experimentally determined geometries is obtained. The complexes of interest include group IVB (Ti, Zr and Hf) and group VB (Nb and Ta) alkylidenes with hydride ligands as well as models for the four-coordinate, olefin metathesis catalysts (Mo-, W-, and Re-alkylidenes) which have been recently synthesized and characterized. In light of the fact that much of the discussion concerning the reactivity of transition-metal carbene complexes has been presented in terms of the resonance contributors derived from rearranging the electrons in the M-C σ and π orbitals, the minima obtained from the portion of the study are then subjected to a further procedure to calculate these contributions. Resonance structures in which the carbon is the negative end of the M-C bond (i.e., nucleophilic resonance structures) contribute 50% to the ground-state wave function of these complexes. Those in which the carbon is formally neutral account for much of the remainder (45%). Only 5% is comprised of electrophilic resonance structures, i.e., those in which the carbon is the positive end of the M-C bond. Furthermore, the metal-carbon double bond is predominantly comprised of five resonance structures. Four of these resonance structures correspond to models of carbene bonding which have been discussed previously in the literature. The other resonance structure, which contributes roughly 33% to the ground-state wave function, has hitherto not been considered when examining the chemical reactivity of carbenes. This large resonance contributor can be described as arising from a dative carbon-to-metal σ bond plus a covalent M-C π bond. digital.library.unt.edu/ark:/67531/metadc107773/
- The Reciprocal Links between Evolutionary-Ecological Sciences and Environmental Ethics
- This article discusses the reciprocal links between evolutionary-ecological sciences and environmental ethics. Confronted with the current environmental crisis, the academic community faces a conceptual and practical problem of dissociation: Ecologists approach nature with the aim of understanding it, whereas environmental ethicists approach nature asking how we should relate to it, or inhabit it. Ecology looks for the "is" of nature, and environmental ethics seeks an "ought" with respect to nature. How can these still largely disconnected and yet parallel courses be bridged? How can the is of ecologists and the ought of eco-philosophers be interrelat-ed? More basically, how can the links between the cognitive-scientific and the practical-ethical spheres be recovered? In this article, the author illustrates the reciprocal relationships between sciences and environmental ethics by examining the Darwinian theory of evolution and discussing its implications for ecologists and ethicists. digital.library.unt.edu/ark:/67531/metadc130190/
- [Review] Chemistry of Advanced Materials: An Overview
- This book review discusses 'Chemistry of Advanced Materials: An Overview', edited by Leonard V. Interrante from Renssalaer Polytechnic Institute, and Mark J. Hampden-Smith from the University of New Mexico. digital.library.unt.edu/ark:/67531/metadc107798/
- [Review] Deciphering the Chemical Code: Bonding Across the Periodic Table
- This book review discusses 'Deciphering the Chemical Code: Bonding Across the Periodic Table' by Nicolaos D. Epiotis from the University of Washington. The reviewer describes the work as a new theoretical framework for describing chemical bonding and gives specific information on what's covered in the book, the themes, and ideal audiences. digital.library.unt.edu/ark:/67531/metadc107796/
- Scanning tunneling microscopy of the electronic structure of chemical vapor deposited diamond films
- This article discusses scanning tunneling microscopy of the electronic structure of chemical vapor deposited diamond films. Scanning tunneling microscopy has been used to characterize the electronic structure and surface morphology of diamond films grown using the hot filament and microwave plasma chemical vapor deposition techniques. The authors observe a significant difference between the current-voltage (I-V) curves for the two types of films. The I-V curves for the hot-filament grown films are characterized by a well-defined zero-current region from which a surface band gap of 4.1 eV is measured. The I-V curves for the microwave plasma grown films exhibit a rectifying behavior which can be modeled by surface band bending. The authors compare the surface density of states obtained from the I-V curves with those obtained from x-ray photoelectron and appearance potential spectroscopies. digital.library.unt.edu/ark:/67531/metadc84361/
- Simultaneous measurement of the average ion-induced electron emission yield and the mean charge for isotachic ions in carbon foils
- This article discusses simultaneous measurement of the average ion-induced electron emission yield and the mean charge for isotachic ions in carbon foils. Knowledge of the incident ion's atomic number (Z₁) dependence of ion-induced electron emission yields can be the basis for a general understanding of ion-atom interaction phenomena and, in particular, for the design of Z₁-sensitive detectors that could be useful, for example, in the separation of isobars in accelerator mass spectrometry. The Z₁ dependence of ion-induced electron emission yields, y, has been investigating using heavy ions C³⁺, O³⁺, F³⁺, Na³⁺, Al³⁺, Si³⁺, P³⁺, S³⁺, Cl³⁺, K³⁺, Ti³⁺, Cr³⁺, Mn⁴⁺, Fe⁴⁺, Co⁴⁺, Ni⁴⁺, Cu⁴⁺, Ga⁴⁺, As⁵⁺, Br⁵⁺, Ru⁷⁺, Ag⁷⁺, Sn⁷⁺, and I⁸⁺ of identical velocity (v = 2v₀, where v₀ is the Bohr velocity) normally incident on 50 μg/cm² sputter-cleaned carbon foils. Measured yields as a function of Z₁ reveal an oscillatory behavior with pronounced maxima and minima. Contrary to previously reported yields that assumed to monotonically increasing empirical mean charge state for the exiting ion, the present work indicates the Z₁ oscillations in the experimentally measured yields, a fact masked in previous work. The strong Z₁ oscillations can only be observed by simultaneous measurement of the yield and the mean charge state. digital.library.unt.edu/ark:/67531/metadc146596/
- Site correlation, anomalous diffusion, and enhancement of the localization length
- This article discusses site correlation, anomalous diffusion, and enhancement of localization length. Herein the authors study the effects on Anderson localizations of correlations in the energy distribution of the sites of a tight-binding Hamiltonian. The lattice correlations are introduced are introduced by means of classical maps generating anomalous diffusion, that have recently been found to account for the correlated disorder of "biological" lattices. The authors show that the enhancement of localization length takes place on a much wider band of energies than in the case of the random-dimer model if the random walk on the site energies of the tight-binding Hamiltonian is determined by the joint action of short- and long-range correlations. digital.library.unt.edu/ark:/67531/metadc139487/
- Small Molecule Elimination from Group IVB (Ti, Zr, Hf) Amido Complexes
- This article discusses small molecule elimination from group IVB (Ti, Zr, Hf) amido complexes. An ab initio quantum chemical analysis of HX (X = H, CH₃, Cl, NH₂, SiH₃) elimination by group IVB (Ti, Zr, Hf) amidos (H₂(X)M - NH₂ → H₂M = NH + HX), of interest in the context of CVD precursor design, is reported. Several deductions may be drawn from the calculations. First, in the transition state (TS) for HX elimination, electropositive and electroneutral X give rise to metal-transannular hydrogen (Ht) distances only slightly longer than normal metal-terminal hydride bonds lengths, while electronegative X groups yield substantially longer MHt distances. Second, the HX elimination barrier (∆Hǂelim) is lower when HX is polarized Hδ- • Hδ+ (X = SiH₃) or nonpolar (X = H). Third, a plot of calculated ∆Hǂelim versus MHt distances in the TS. Fourth, analysis of the electronic structure along the intrinsic reaction coordinate (IRC) supports the importance of N-H•••M agostic interactions preceding N-H scission. Fifth, the IRC shows the MHt distance decreasing as Ht is transferred from N to X, reaching a minimum when the transfer is roughly half complete, and then increasing once more is HX is eliminated. These results point to the leaving group (X) playing a crucial role in tuning the bonding the energetics of the TS, and thus the rate of HX elimination. The results lead to the conclusion that materials precursors designed to enhance MHt interaction, through the intermediacy of X, in the TS and along the reaction coordinate will lead to lower activation barriers to XH elimination. digital.library.unt.edu/ark:/67531/metadc107776/
- Structural Dichotomy in Six-Coordinate d⁰ Complexes: Trigonal Prismatic (ᵗBu₃SiC≡C)₆Ta⁻ and Octahedral (ᵗBu₃SiC≡C)₆M²⁻ (M = Zr, Hf)
- This article discusses structural dichotomy in six-coordinate d⁰ complexes. Utilization of the bulky acetylide, ᵗBu₃SiC≡C⁻, enabled the synthesis of several early metal polyacetylides. Addition of NaC≡CH to ᵗBu₃SiBr in dimethyl sulfoxide afforded ᵗBu₃SiC≡CH, which was deprotonated to yield ᵗBu₃SiC≡CLi. Treatment of ZrCl₄, HfCl₄, adn TaCl₅ with varying amounts of ᵗBu₃SiC≡CLi gave {(THF)₂Li(ᵗBu₃SiC≡C)₂}Zr(C≡CSiᵗBu₃)₃(THF) (1; THF = tetrahydrofuran), {Et₂O)Li(ᵗBu₃SiC≡C)₂}Hf(C≡CSiᵗBu₃)₃(OEt₂) (2), {Li(ᵗBu₃SiC≡C)₃}₂M(M = Zr, 6; Hf, 7), and {Li(ᵗBu₃SiC≡C)₃}Ta(C≡CSiᵗBu₃)₃ (3). Metathesis of 3 with KOTf generated KTa(C≡CSiᵗBu₃)₆ (4) and cation sequestration of 4 with crypt 2.2.2 provided [K(crypt 2.2.2)][Ta(C≡CSiᵗBu₃)₆](5). Single-crystal X-ray structural studies determined the structures (core symmetry) of 1 (Oh), 2, (Oh), 3 (D₃), 5 (D₃), 6 (Oh), and 7 (Oh). The D₃h to D₃ twist in 3 and 5 has a steric origin, and the counterion position appears inconsequential. Origins of the structural preferences illustrated by the dichotomous twisted trigonal prismatic and octahedral cores of the d⁰ hexaacetylides 5 and 6 were probed through density functional (ADF) and effective core potential (GAMESS) calculations. The structural difference results from a lessening electronic preference for the trigonal prism-primarily a greater HOMO/LUMO gap-upon moving from Ta to Zr, minor steric factors, and increased interligand repulsions in the dianion (VSEPR). digital.library.unt.edu/ark:/67531/metadc107797/
- Theoretical Estimation of Vibrational Frequencies Involving Transition Metal Compounds
- This article discusses the theoretical estimation of vibrational frequencies involving transition metal compounds. The reliability of effective core potentials (ECPs) for estimating vibrational frequencies of transition metal (TM) complexes is assessed in relation to all-electron methods for main group compounds. Complexes with a multiple bond between a transition metal and chalcogen (O,S, or Se), chalcogenides, are investigated using the Stevens ECP/valence basis set scheme. Statistical treatment of the data indicates that ECPs, in addition to reliably modeling electronic structure, can be successful in estimating vibrational frequencies for TM complexes. As expected, theoretical prediction of vibrational data is not as accurate as the prediction of metric data for chalcogenides. However, agreement with experiment is still very good at the Hartree-Fock level of theory and is in even better accord upon the use of simple correlations to model well-known computational deficiencies (e.g., the neglect of anharmonic effects). Analysis of the data show interesting differences in predictive ability for first row transition metals versus second- and third-row analogues and oxo complexes versus their congeners with heavier chalcogens. digital.library.unt.edu/ark:/67531/metadc107803/
- Toxicological Case Study of Dallas' Central Wastewater Treatment Plant Effluent and Ambient Trinity River Samples: 1989, 1990, 1991
- "This study was implemented voluntarily by personnel at Dallas Water Utilities in response to concerns that the Dallas Central Wastewater Treatment Plant was adversely affecting downstream water quality." The treatment plant was studied to determine whether it was "discharging toxic materials in toxic amounts to the Trinity River" (p. 1). digital.library.unt.edu/ark:/67531/metadc29402/
- Transition Metal Imido Complexes
- This articles discusses transition metal imido complexes. A wide range of transition metal imido (TMI) complexes is studied using ab initio molecular orbital (MO) calculations. The main computational point of interest is the further testing of effective core potentials (ECPs) and valence basis sets to allow for the accurate calculation of properties for reasonably sized transition metal complexes. On the chemical side, several results from the study are to be noted. The agreement between geometries for calculated models and their experimental counterparts ranges from very good to excellent, as found in previous studies of multiply bonded transition metal-group IVA complexes. Taken together, these data suggest that the accuracy one has come to expect for the prediction of structural properties for main-group compounds may yet become a reality for transition metal complexes. The correct prediction of molecular structure also leads one to infer that the bonding in these complexes is also accurately described. The MC/LMO/CI (multiconfigurational/localized MO/configuration interaction) technique shows that eight resonance structures are most significant in the description of the metal-imido linkage. Three of these account for roughly two-thirds of the total contributions; two resonance structures, both possessing a dative σ bond, correspond to novel bonding descriptions for TMI complexes. The dative character of the σ bond has been largely unappreciated. The MC/LMO/CI results also indicate that the metal-imido bond is intermediate between a double and a triple bond. Nucleophilic resonance structures decrease as one goes to the right in the transition series while electrophilic ones show the reverse behavior, in agreement with observed reactivity. digital.library.unt.edu/ark:/67531/metadc107775/