Search Inside the UNT College of Arts and Sciences

  You limited your search to:

  Partner: UNT College of Arts and Sciences
Event-Driven Power-Law Relaxation in Weak Turbulence
This article discusses event-driven power-law relaxation in weak turbulence. Abstract: We characterize the spectral properties of weak turbulence in a liquid crystal sample driven by an external electric field, as a function of the applied voltage, and we find a 1/f noise spectrum S(f) ∝ 1/fn within the whole range 0< ɳ <2. We theoretically explore the hypothesis that the system complexity is driven by non-Poisson events resetting the system through creation and annihilation of coherent structures, retaining no memory of previous history (crucial events). The authors study the time asymptotic regime by means of the density ψ(τ) of the time distances between two crucial events, yielding ɳ = 3 - μ, where μ is defined through the long-time form ψ(τ) ∝ 1/τµ, with 1 < µ < 3. The system regression to equilibrium after an abrupt voltage change experimentally confirms the theory, proving violations of the ordinary linear response theory for both ɳ > 1 and ɳ < 1. digital.library.unt.edu/ark:/67531/metadc40395/
Experimental Quenching of Harmonic Stimuli: Universality of Linear Response Theory
This article discusses experimental quenching of harmonic stimuli. Abstract: We show that liquid crystals in the weak turbulence electroconvective regime respond to harmonic perturbations with oscillations whose intensity decay with an inverse power law of time. We use the results of this experiment to prove that this effect is the manifestation of a form of linear response theory (LRT) valid in the out-of-equilibrium case, as well as at thermodynamic equilibrium where it reduces to the ordinary LRT. We argue that this theory is a universal property, which is not confined to physical processes such as turbulent or excitable media, and that it holds true in all possible conditions, and for all possible systems, including a complex networks, thereby establishing a bridge between statistical physics and all the fields of research in complexity. digital.library.unt.edu/ark:/67531/metadc40394/
Fluctuation-Dissipation Theorem for Event-Dominated Processes
This article discusses fluctuation-dissipation theorem for event-dominated processes. Abstract: We study a system whose dynamics are driven by non-Poisson, renewal, and nonergodic events. We show that external perturbations influencing the times at which these events occur violate the standard fluctuation-dissipation prescription due to renewal aging. The fluctuation-dissipation relation of this Letter is shown to be the linear response limit of an exact expression that has been recently proposed to account for the luminescence decay in a Gibbs ensemble of semiconductor nanocrystals, with intermittent fluorescence. digital.library.unt.edu/ark:/67531/metadc40397/
An IRE-Like AGC Kinase Gene, MtIRE, Has Unique Expression in the Invasion Zone of Developing Root Nodules in Medicago truncatula
This article discusses AGC kinase genes. Abstract: The AGC protein kinase family (cAMP-dependent protein kinases A, cGMP-dependent protein kinases G, and phospholipid-dependent protein kinases C) have important roles regulating growth and development in animals and fungi. They are activated via lipid second messengers by 3-phosphoinositide-dependent protein kinase coupling lipid signals to phosphorylation of the AGC kinases. These phosphorylate downstream signal transduction protein targets. AGC kiinases are becoming better studied in plants, especially in Arabidopsis (Arabidopsis thaliana), where specific AGC kinases have been shown to have key roles in regulating growth signal pathways. The authors report here the isolation and characterization of the first AGC kinase gene identified in Medicago truncatula, MtIRE. It was cloned by homology with the Arabidopsis INCOMPLETE ROOT HAIR ELONGATION (IRE) gene. Semiquantitative reverse transcription-polymerase chain reaction analysis shows that, unlike its Arabidopsis counterpart, MtIRE is not expressed in uninoculated roots, but is expressed in root systems that have been inoculated with Sinorhizobium meliloti and are developing root nodules. MtIRE expression is also found in flowers. Expression analysis of a time course of nodule development and of nodulating root systems of many Medicago nodulation mutants shows MtIRE expression correlates with infected cell maturation during nodule development. During the course of these experiments, nine Medicago nodulation mutants, including sli and dnf1 to 7 mutants, were evaluated for the first time for their microscopic nodule phenotype using S. meliloti constitutively expressing lacZ. Spatial localization of a pMtIRE-gusA transgene in transformed roots of composite plants showed that MtIRE expression is confined to the proximal part of the invasion zone, zone II, found in indeterminate nodules. This suggests MtIRE is useful as an expression marker for this region of the invasion zone. digital.library.unt.edu/ark:/67531/metadc40389/
LIN, a Medicago truncatula Gene Required for Nodule Differentiation and Persistence of Rhizobial Infections
This article discusses LIN, a Medicago truncatula gene. Abstract: Ethyl methanesulfonate mutagenesis of the model legume Medicago truncatula has previously identified several genes required for early steps in nodulation. Here, the authors describe a new mutant that is defective in intermediate steps of nodule differentiation. The lin (lumpy infections) mutant is characterized by a 4-fold reduction in the number of infections, all of which arrest in the root epidermis, and by nodule primordia that initiate normally but fail to mature. Genetic analyses indicate that the symbiotic phenotype is conferred by a single gene that maps to the lower arm of linkage group 1. Transcriptional markers for early Nod factor responses (RIP1 and ENOD40) are induced in lin, as is another early nodulin, ENOD20, a gene expressed during the differentiation of nodule primordia. By contrast, other markers correlated with primordium differentiation (CCS52A), infection progression (MtN6), or nodule morphogenesis (ENOD2 and ENOD8) show reduced or no induction in homozygous lin individuals. Taken together, these results suggest that LIN functions in maintenance of rhizobial infections and differentiation of nodules from nodule primordia. digital.library.unt.edu/ark:/67531/metadc40388/
Absorption and Emission in the Non-Poissonian Case
This article discusses absorption and emission in the Non-Poissonian Case. Abstract: This Letter addresses the challenging problems posed to the Kubo-Anderson (KA) theory by the discovery of intermittent resonant fluorescence with a nonexponential distribution of waiting times. We show how to extend the KA theory from aged to aging systems, aging for a very extended time period or even forever, being a crucial consequence of non-Poisson statistics. digital.library.unt.edu/ark:/67531/metadc67641/
Aging and Rejuvenation with Fractional Derivatives
This article discusses aging rejuvenation with fractional derivatives. Abstract: We discuss a dynamic procedure that makes a fractional derivatives emerge in the time asymptotic limit of non-Poisson processes. We find that two-state fluctuations, with an inverse power-law distribution of waiting times, finite first moment, and divergent second moment, namely, with the power index μ in the interval 2<μ<3, yield a generalized master equation equivalent to the sum of an ordinary Markov contribution and a fractional derivative term. We show that the order of the fractional derivative depends on the age of the process under study. If the system is infinitely old, the order of the fractional derivative, o, is given by o=3-μ. A brand new system is characterized by the degree o=μ-2. If the system is prepared at time -tₐ<0 and the observation begins at time t=0, we derive the following scenario. For times 0<t«tₐ the system is satisfactorily described by the fractional derivative with o=3-μ. Upon time increase the system undergoes a rejuvenation process that in the time limit t⪢tₐ yields o=μ-2. The intermediate time regime is probably incompatible with a picture based on fractional derivatives, or, at least, with a mono-order fractional derivative. digital.library.unt.edu/ark:/67531/metadc67638/
What's Wrong with Processed Food?
This presentation is part of the faculty lecture series UNT Speaks Out on the Food We Eat. The topics include what processed food is, genetically-modified foods, functional foods, and the impacts of processed foods. digital.library.unt.edu/ark:/67531/metadc67609/
Diffusion Entropy and Waiting Time Statistics of Hard-X-Ray Solar Flares
This article discusses diffusion entropy and waiting time statistics of hard-x-ray solar flares. Abstract: We show at work a technique of scaling detection based on evaluating the Shannon entropy of the diffusion process obtained by converting the time series under study into trajectories. This method, called diffusion entropy, affords information that cannot be derived from the direct evaluation of waiting times. We apply this method to the analysis of the distribution of time distance τ between two nearest-neighbor solar flares. This traditional part of the analysis is based on the direct evaluation of the distribution function ψ(τ), or of the probability ψ(τ), that no time distance smaller than a given τ is found. We adopt the paradigm of the inverse power-law behavior, and the authors focus on the determination of the inverse power index μ, without ruling out different asymptotic properties that might be revealed, at larger scales, with the help of richer statistics. We then use the DE method, with three different walking rules, and the authors focus on the regime of transition to scaling. This regime of transition and the value of the scaling parameter itself, δ, depends on the walking rule adopted, a property of interest to shed light on the slow process of transition from dynamics to thermodynamics often occurring under anomalous statistical conditions. With the first two rules the transition regime occurs through-out a large time interval, and the information contained in the time series is transmitted, to a great extent, to it, as well as to the scaling regime. By using the third rule, on the contrary, the same information is essentially conveyed to the scaling regime, which, in fact, emerges very quickly after a fast transition process. We show that the DE method not only causes to emerge the long-range correlation with a given μ<3, and so a basin of attraction different from the ordinary Gaussian one, but it also reveals the presence of memory effects induced by the time dependence of the solar flare rate. When this memory is annihilated by shuffling, the scaling parameter δ is shown to fit the theoretically expected function of μ. All this leads us to the compelling conclusion that μ=2.138±0.01. digital.library.unt.edu/ark:/67531/metadc67629/
Scaling Detection in Time Series: Diffusion Entropy Analysis
This article discusses scaling detection in time series. The methods currently used to determine the scaling exponent of a complex dynamic process described by a time series are based on the numerical evaluation of variance. This means that all of them can be safely applied only to the case where ordinary statistical properties hold true even if strange kinetics are involved. The authors illustrate a method of statistical analysis based on the Shannon entropy of the diffusion process generated by the time series, called diffusion entropy analysis (DEA). The authors adopt artificial Gauss and Lévy time series, as prototypes of ordinary and anomalous statistics, respectively, and the authors analyze them with the DEA and four ordinary methods of analysis, some of which are very popular. The authors show that the DEA determines the correct scaling exponent even when the statistical properties, as well as the dynamic properties, are anomalous. The other four methods produce correct results in the Gauss case but fail to detect the correct scaling in the case of Lévy statistics. digital.library.unt.edu/ark:/67531/metadc67632/
Random Growth of Interfaces as a Subordinated Process
In this article, the authors study the random growth of surfaces from within the perspective of a single column, namely, the fluctuation of the column height around the mean value, y(τ)=h(τ)-‹h(τ)›, which is depicted as being subordinated to a standard fluctuation-dissipation process with friction y. The authors argue that the main properties of Kardar-Parisi-Zhang theory, in one dimension, are derived by identifying the distribution of return times to y(0)=0, which is a truncated inverse power law, with the distribution of subordination times. The agreement of the theoretical prediction with the numerical treatment of the (1+1)-dimensional model of ballistic deposition is remarkably good, in spite of the finite-size effects affecting this model. digital.library.unt.edu/ark:/67531/metadc67637/
Scaling Breakdown: A Signature of Aging
In this article, the authors prove that the Lévy walk is characterized by bilinear scaling. This effect mirrors the existence of a form of aging that does not require the adoption of nonstationary conditions. digital.library.unt.edu/ark:/67531/metadc67630/
Vortex Dynamics in Evolutive Flows: A Weakly Chaotic Phenomenon
In this article, the authors make use of a wavelet method to extract, from experimental velocity signals obtained in an evolutive flow, the dominating velocity components generated by vortex dynamics. The authors characterize the resulting time series complexity by means of a joint use of data compression and of an entropy diffusion method. The authors assess that the time series emerging from the wavelet analysis of the vortex dynamics is a weakly chaotic process with a vanishing Kolmogorov-Sinai entropy and a power-law growth of the information content. To reproduce the Fourier spectrum of the experimental signal, the authors adopt a harmonic dependence on time with a fluctuating frequency, ruled by an inverse power-law distribution of random events. The complexity of these fluctuations is determined by studying the corresponding artificial sequences. The authors reproduce satisfactorily both spectral and complex properties of the experimental signal by locating the complexity of the fluctuating process at the border between the stationary and the nonstationary states. digital.library.unt.edu/ark:/67531/metadc67634/
Power-Law Time Distribution of Large Earthquakes
In this article, the authors study the statistical properties of time distribution of seismicity in California by means of a new method of analysis, the diffusion entropy. The authors find that the distribution of time intervals between a large earthquake (the main shock of a given seismic sequence) and the next one does not obey Poisson statistics, as assumed by the current models. The authors prove that this distribution is an inverse power law with an exponent μ = 2.06 ± 0.01. The authors propose the long-range model, reproducing the main properties of the diffusion entropy and describing the seismic triggering mechanisms induced by large earthquakes. digital.library.unt.edu/ark:/67531/metadc67639/
Solar Turbulence in Earth's Global and Regional Temperature Anomalies
This article presents a study of the influence of solar activity on the earth's temperature. In particular, the authors focus on the repercussion of the fluctuations of the solar irradiance on the temperature of the Northern and Southern hemispheres as well as on land and ocean regions. While solar irradiance data are not directly analyzed, the authors make use of a published solar irradiance reconstruction for long-time-scale fluctuations, and for short-time-scale fluctuations the authors hypothesize that solar irradiance and solar flare intermittency are coupled in such a way that the solar flare frequency fluctuations are stochastically equivalent to those of the solar irradiance. The analysis is based upon wavelet multiresolution techniques and scaling analysis methods for processing time series. The limitations of the correlation analysis applied to the short-time-scale fluctuations are discussed. The scaling analysis uses both the standard deviation and the entropy of the diffusion generated by the temperature signals. The joint use of these two scaling methods yields evidence of a Levy component in the temporal persistence of the temperature fluctuations within the temporal range from a few weeks to a few years. This apparent Levy persistence of the temperature fluctuations is found, by using an appropriate model, to be equivalent to the Levy scaling of the solar flare intermittency. The mean monthly temperature data sets cover the period from 1856 to 2002. digital.library.unt.edu/ark:/67531/metadc67636/
Mega et al. Reply
This article is a reply to a comment by A. Helmstetter and D. Sornette about the article 'Power-Law Time Distribution of Large Earthquakes' from 2003. digital.library.unt.edu/ark:/67531/metadc67640/
Quantum Entanglement and Entropy
This article discusses quantum entanglement and entropy. Entanglement is the fundamental quantum property behind the now popular field of quantum transport of information. This quantum property is incompatible with the separation of a single system into two uncorrelated subsystems. Consequently, it does not require the use of an additive form of entropy. The authors discuss the problem of the choice of the most convenient entropy indicator, focusing their attention on a system of two qubits, and on a special set, denoted by ℑ. This set contains both the maximally and partially entangled states that are described by density matrices diagonal in the Bell basis set. The authors select this set for the main purpose of making their work of analysis more straightforward. As a matter of fact, the authors find that in general the conventional von Neumann entropy is not a monotonic function of the entanglement strength. This means that the von Neumann entropy is not a reliable indicator of the departure from the condition of maximum entanglement. The authors study the behavior of a form of nonadditive entropy, made popular by the 1988 work by Tsallis [J. Stat. Phys. 52, 479 (1988)]. The authors show that in the set ℑ, implying the key condition of nonvanishing entanglement, this nonadditive entropy indicator turns out to be a strictly monotonic function of the strength of the entanglement, if entropy indexes q larger than a critical value Q are adopted. The authors argue that this might be a consequence of the nonadditive nature of the Tsallis entropy, implying that the world is quantum and that uncorrelated subsystems do not exist. digital.library.unt.edu/ark:/67531/metadc67627/
Memory Beyond Memory in Heart Beating, a Sign of a Healthy Physiological Condition
In this article, the authors describe two types of memory and illustrate each using artificial and actual heartbeat data sets. The first type of memory, yielding anomalous diffusion, implies the inverse power-law nature of the waiting time distribution and the second the correlation among distinct times, and consequently also the occurrence of many pseudoevents, namely, not genuinely random events. Using the method of diffusion entropy analysis, the authors establish the scaling that would be determined by the real events alone. The authors prove that the heart beating of healthy patients reveals the existence of many more pseudoevents than in the patients with congestive heart failure. digital.library.unt.edu/ark:/67531/metadc67628/
Do I Look Illegal? Undocumented Latino/a Students and the Challenges of Life in the Shadows
This presentation is part of the faculty lecture series UNT Speaks Out on Unauthorized Immigration. This presentation discusses illegal immigration and the challenges for undocumented Latino/a students. digital.library.unt.edu/ark:/67531/metadc67614/
Generalized Master Equation Via Aging Continuous-Time Random Walks
This article discusses generalized master equation via aging continuous-time random walks. Abstract: We discuss the problem of the equivalence between continuous-time random walk (CTRW) and generalized master equation (GME). The walker, making instantaneous jumps from one site of the lattice to another, resides in each site for extended times. The sojourn times have a distribution density ψ(t) that is assumed to be an inverse power law with the power index μ. We assume that the Onsager principle is fulfilled, and we use this assumption to establish a complete equivalence between GME and the Montroll-Weiss CTRW.We prove that this equivalence is confined to the case where ψ(t) is an exponential. We argue that is so because the Montroll-Weiss CTRW, as recently proved by Barkai [E. Barkai, Phys. Rev. Lett. 90, 104101 (2003)], is nonstationary, thereby implying aging, while the Onsager principle is valid only in the case of fully aged systems. The case of a Poisson distribution of sojourn times is the only one with no aging associated to it, and consequently with no need to establish special initial conditions to fulfill the Onsager principle. We consider the case of a dichotomous fluctuation, and we prove that the Onsager principle is fulfilled for any form of regression to equilibrium provided that the stationary condition holds true. We set the stationary condition on both the CTRW and the GME, thereby creating a condition of total equivalence, regardless of the nature of the waiting-time distribution. As a consequence of this procedure the authors create a GME that is a bona fide master equation, in spite of being non-Markov. We note that the memory kernel of the GME affords information on the interaction between system of interest and its bath. The Poisson case yields a bath with infinitely fast fluctuations. We argue that departing from the Poisson form has the effect of creating a condition of infinite memory and that these results might be useful to shed light on the problem of how to unravel non-Markov quantum master equations. digital.library.unt.edu/ark:/67531/metadc67635/
Lévy Scaling: The Diffusion Entropy Analysis Applied to DNA Sequences
This article discusses Lévy scaling and the diffusion entropy analysis applied to DNA sequences. Abstract: We address the problem of the statistical analysis of a time series generated by complex dynamics with the diffusion entropy analysis (DEA) [N. Scafetta, P. Hamilton, and P. Grigolini, Fractals 9, 193 (2001)]. This method is based on the evaluation of the Shannon entropy of the diffusion process generated by the time series imagined as a physical source of fluctuations, rather than on the measurement of the variance of this diffusion process, as done with the traditional methods. We compare the DEA to the traditional methods of scaling detection and prove that the DEA is the only method that always yields the correct scaling value, if the scaling condition applies. Furthermore, DEA detects the real scaling of a time series without requiring any form of detrending. We show that the joint use of DEA and variance method allows to assess whether a time series is characterized by Lévy or Gauss statistics. We apply the DEA to the study of DNA sequences and prove that their large-time scales are characterized by Lévy statistics, regardless of whether they are coding or noncoding sequences. We show that the DEA is a reliable technique and, at the same time, we use it to confirm the validity of the dynamic approach to the DNA sequences, proposed in earlier work. digital.library.unt.edu/ark:/67531/metadc67631/
Linear Response to Perturbation of Nonexponential Renewal Processes
This article discusses the linear response to perturbation of nonexponential renewal processes. Abstract: We study the linear response of a two-state stochastic process, obeying the renewal condition, by means of a stochastic rate equation equivalent to a master equation with infinite memory. We show that the condition of perennial aging makes the response to coherent perturbation vanish in the long-time limit. digital.library.unt.edu/ark:/67531/metadc67626/
Long- and Short-Time Analysis of Heartbeat Sequences: Correlation with Mortality Risk in Congestive Heart Failure Patients
This paper discusses long- and short-time analysis of heartbeat sequences and the correlation with mortality risk in congestive heart failure patients. Abstract: We analyze RR heartbeat sequences with a dynamic model that satisfactorily reproduces both the long- and the short-time statistical properties of heart beating. These properties are expressed quantitatively by means of two significant parameters, the scaling δ concerning the asymptotic effects of long-range correlation, and the quantity 1 - π establishing the amount of uncorrelated fluctuations. We find a correlation between the position in the phase space (δ,π) of patients with congestive heart failure and their mortality risk. digital.library.unt.edu/ark:/67531/metadc67633/
Calculations of the Relative Energies of the 2B1g and 2A2u States of Cyclobutanetetraone Radical Cation and Radical Anion Provide Further Evidence of a 3B2u Ground State for the Neutral Molecule: A Proposed Experimental Test of the Prediction of a Triplet Ground State for (CO)4
This article discusses ground states. Abstract: B3LYP, CCSD(T), and CASPT2 calculations with the 6-311+G(2df) basis set have been performed on the radical anion and radical cation of cyclobutanetetraone (1). The very similar energies computed for the 2B1g and 2A2u states of both 1·+ and 1·- indicate that the singly occupied b1g and a2u MOs in these two states of the radical cation and anion have nearly the same energies, thus supporting the previously made prediction that neutral 1 has a 3B2u ground state. Reaction of squaric acid with O.(-), followed by negative ion photoelectron spectroscopy (NIPES) on the 1.(-) thus formed, is proposed as an experimental test of the startling prediction that tetraketone (1), a molecule that would be expected to be a closed-shell singlet, actually has a triplet ground state. digital.library.unt.edu/ark:/67531/metadc71812/
Calculations Predict That Carbon Tunneling Allows the Degenerate Cope Rearrangement of Semibullvalene to Occur Rapidly at Cryogenic Temperatures
This article discusses carbon tunneling. Abstract: Calculations on the role of tunneling in the degenerate Cope rearrangements of semibullvalene (1) and barbaralane (3) predict that, at temperatures below 40 K, tunneling from the lowest vibrational level should make the temperature-independent rate constants k = 1.43 x 10(-3) s(-1) and k = 7.28 x 10(-9) s(-1), respectively. An experiment, using semibullvalene-2(4)-d1, is proposed to test the prediction of rapid tunneling by 1 at cryogenic temperatures. digital.library.unt.edu/ark:/67531/metadc71814/
Calculations Predict a Large Inverse H/D Kinetic Isotope Effect on the Rate of Tunneling in the Ring Opening of Cyclopropylcarbinyl Radical
This article discusses calculations that predict a large inverse H/D kinetic isotope effect. Abstract: Tunneling rates are expected to decrease exponentially with the square root of the effective tunneling mass. Therefore, on substitution of a heavier for a lighter isotope, the observation of a large kinetic isotope effect (KIE), involving a substantial decrease in rate constant, is a commonly used diagnostic for a large contribution from quantum mechanical tunneling to a reaction. However, in this communication, the authors report the results of calculations that make the opposite prediction about some of the KIEs on the ring opening of cyclopropylcarbinyl radical (1) to 3-butene-1-y1 radical (2) by tunneling at cryogenic temperatures. Substitution of a heavier for a lighter isotope at the radical center (C1) of 1 is calculated to accelerate the rate of tunneling, giving KIEs at this carbon that are inverse. Of particular note is the authors' prediction that substitution of deuterium for both hydrogens at C1 will lead to a nearly 3-fold increase in the rate of reaction at temperatures so low that ring opening proceeds exclusively by tunneling from the lowest vibrational level. digital.library.unt.edu/ark:/67531/metadc71808/
Cyclooctatetraenes Tetrakis-Annelated with α-Dithio- or α-Diselenocarbonyl Groups: Diradicals Predicted To Have Ground States with 10 π Electrons in the Eight-Membered Ring and Two-Center, Three-Electron, σ Bonds between Two Pairs of Chalcogen Atoms
This article discusses cyclooctatetraenes. Abstract: (U)B3LYP calculations with the 6-31+G(d) and 6-311+G(2df) basis sets have been carried out on cyclooctatetraenes 6 and 7, in which the COT ring is tetrakis-annelated with α-dithio- or α-diselenocarbonyl groups. Transferring two electrons from the high-lying b1g and eu σ MOs in 6 and 7 into the unoccupied, nonbonding, COT π orbital is computed to be energetically favorable. The lowest D4h electronic state is calculated to be 3Eu, which formally contains 10 π electrons in the eight-membered ring and has two unpaired electrons in σ MOs. The 3Eu state undergoes a first-order Jahn-Teller distortion to form 6d and 7d, in which the pair of one-electron holes in the σ MOs is stabilized by the formation of two, two-center, three-electron bonds between pairs of chalcogen atoms that are diagonally across the eight-membered ring from each other. The corresponding open-shell singlets are computed to be about 1 kcal/mol lower in energy than the Jahn-Teller distorted triplets. Molecules 6i and 7i, in which the C-C bond in one four-membered ring is cleaved, are computed to be lower in energy than 6d and 7d. However, a substantial barrier is predicted to separate each of the two pairs of isomers so that 6d and 7d should, at least in principle, be isolable. digital.library.unt.edu/ark:/67531/metadc71813/
Current Applications of Computational Chemistry in JACS - Molecules, Mechanisms, and Materials
This article discusses current applications of computational chemistry. This virtual issue of JACS Select is devoted to some of the computation chemistry that has recently been published in the Journal of the American Chemical Society (JACS). The 25 articles and Communications that appear in this issue of JACS Select were chosen on the basis of the enthusiasm of the referees for these manuscripts when they were reviewed, as well as on the number of times each of these articles has been accessed online since its publication. Diversity of subject matter was not a criterion used in selecting these 25 articles from the ca. 50 well-reviewed, frequently accessed articles that were initially considered. However, inspection of the list of the subjects covered - from amyloid fibril polymorphism to nucleation of amorphous calcium carbonate; from the structure of solid Li(NH3)4 to the role that solvation plays in the Thorpe-Ingold effect; and to the nonstatistical, gas-phase dynamics of [1,5] hydrogen shifts in chemically activated cyclopentadiene - reveals the diverse nature of some of the best papers in computational chemistry that have been published recently in JACS. digital.library.unt.edu/ark:/67531/metadc71807/
Current Behavioral and Psychosocial Interventions for HIV/AIDS
This presentation is part of the faculty lecture series UNT Speaks Out on AIDS. This presentation discusses recent directions in psychosocial research on HIV/AIDS in the United States. digital.library.unt.edu/ark:/67531/metadc71782/
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/
Calculating Changes in Worklife Expectancies and Lost Earnings in Personal Injury Cases
This article discusses calculating changes in worklife expectancies and lost earnings in personal injury cases. Abstract: This paper utilizes the Bureau of Labor Statistics (BLS) new worklife tables' information on workforce participation probabilities to estimate the effect of an injury on a worker's life expectancy, worklife expectancy and discounted expected income. After a medical opinion has been obtained concerning the effect of an injury on a worker's probabilities of living and remaining active, the BLS's probability figures can be adjusted and incorporated into a Markov process to estimate the impact of the injury. It is shown that Alter and Becker's technique can be adapted to estimate the present value of the lost expected income. digital.library.unt.edu/ark:/67531/metadc71789/
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/
Cooperative Effects in the Annelation of Benzene by Multiple Etheno Groups
This article discusses cooperative effects in the annelation of benzene by multiple etheno groups. Abstract: The results of B3LYP/6-31G(d) calculations show that there is a strong cooperative effect on the energies that result from annelating benzene with 1, 2, and 3 etheno groups, to form 3, 4, and 5 respectively. The etheno annelation energies have been decomposed into two major contributors - etheno annelation, with all the bonds in the six-membered ring constrained to have the same C-C bond length as in D6h benzene, and optimization of the C-C bond lengths in the annelated benzene ring. The energies computed for each of these two steps show that the etheno groups behave cooperatively in both of them. The origin of the cooperativity, calculated for each step, is described and discussed. digital.library.unt.edu/ark:/67531/metadc71793/
Urban Water Demand Estimates Under Increasing Block Rates
This article discusses urban water demand estimates under increasing block rates. A residential water demand equation is estimated using the only data set on water consumption that contains time series (monthly) observations on individual customers facing an increasing block rate schedule. Because the price of water both determines, and is determined by, usage, ordinary least squares estimation will yield biased estimates. Thus, two-stage least squares and instrumental variables techniques are used. The estimated coefficients on lawn size, weather, house size, and income have the expected signs and are statistically significant. However, there is not any significant response to changes in water price, perhaps due to the relatively low cost of water. digital.library.unt.edu/ark:/67531/metadc71792/
With a Little Help from My Friends: Forty Years of Fruitful Chemical Collaborations
This article discusses collaborations. Over the past 40 years, much of the author's research, both computational and experimental, has involved collaborations. This Perspective describes some of the author's collaborative research in eight different areas of organic and theoretical chemistry: (1) hydrocarbons containing unsaturatively, 1,3-bridged cyclobutane rings, (2) the use of orbital topology for predicting the ground states of diradicals, (3) violations of Hund's rule, (4) the chemistry of phenylnitrenes, (5) tunneling by carbon in organic reactions, (6) the Cope rearrangement and the effect of substituents on it, (7) pyramidalized alkenes, dehydrocubanes, cubyl cation, and octanitrocubane, and (8) the effects of geminal fluorine substitution at C-2 of 1,3-diradicals. Highlighted in this Perspective are the synergism between calculations and experiments in the author's research and the many different roles that serendipity has played in the collaborations that are described herein. digital.library.unt.edu/ark:/67531/metadc71809/
Effects of Geminal Methyl Groups on the Tunnelling Rates in the Ring Opening of Cyclopropylcarbinyl Radical at Cryogenic Temperature
This article discusses the effects of geminal methyl groups on the tunnelling rates in the ring opening of cyclopropylcarbinyl radical at cryogenic temperature. Abstract: CVT + SCT calculations on the rate of tunnelling at 20 K in the ring opening of cyclopropylcarbinyl radical, substituted with geminal methyl groups at a ring carbon (1b), have been performed. The calculations predict that, contrary to expectations based on the effect of mass on the rate of tunnelling, the geminal methyl substituents in 1b should make the rate of ring opening to 1,1-dimethyl-3-butenyl radical (2b) 10(4) times faster than the rate of ring opening of unsubstituted cyclopropylcarbinyl radical (1a) to 3-butenyl radical (2a) and almost 10(6) times faster than the rate of ring opening of 1b to 2,2-dimethyl1-3-butenyl radical (2c). The reasons for these unexpected findings are discussed. digital.library.unt.edu/ark:/67531/metadc71802/
Through-Bond Interactions in the Diradical Intermediates Formed in the Rearrangements of Bicyclo[n.m.0]alkatetraenes
This article discusses through-bond interactions. The intermediates and transition structures in the degenerate thermal rearrangements of bicyclo[4.4.0]deca-2,4,7,9-tetraene (1c), bicyclo[5.5.0]dodeca-2,4,8,10-tetraene(11b), and bicyclo[5.4.0]undeca-2.4.8.10-tetraene (14) have been located by (U)B3LYP/6-31G(d) calculations. The singlet-triplet energy differences (∆Est) in the diradical intermediates (tricyclo[4.4.0.02,7]deca-3,8-dien-5,10-diyl (2c), tricyclo[5.5.0.05,11]dodeca-2,8-dien-4,10-diyl (12b), and tricyclo[5.4.0.05,11]undeca-2,8-dien-4,10-diyl(15)) have been computed, using both UB3LYP and (6/6)CASPT2 calculations. ∆Est in 2c, in which a four-membered ring is anti-bridged by two allylic radicals, is computed to be larger by a factor of 5 than ∆Est in 15, in which the anti-bridged ring is five-membered, and by a factor of 10 than that in 12b, in which the anti-bridged ring is six-membered. The reasons for the much larger interaction between two allylic radicals through the bonds of the four-membered ring in 2c than through the bonds of the five-membered ring in 15 or the six-membered ring in 12b are discussed, and the consequences of the large, through-bond stabilization of the singlet state of 2c are described. digital.library.unt.edu/ark:/67531/metadc71806/
Photoelectron Spectroscopic Study of the Oxyallyl Diradical
This article discusses photoelectron spectroscopic study of the oxyallyl diradical. The photoelectron spectrum of the oxyallyl (OXA) radical anion has been measured. The radical anion has been generated in the reaction of the atomic oxygen radical anion (O߭߫) with acetone. Three low-lying electronic states of OXA have been observed in the spectrum. Electronic structure calculations have been performed for the triplet states (3B2 and 3B1) of OXA and the ground doublet state (2A2) of the radical anion using density functional theory (DFT). Spectral simulations have been carried out for the triplet states based on the results of the DFT calculations. The simulations identifies a vibrational progression of the CCC bending mode of the 3B2 state of OXA in the lower electron binding energy (eBE) portion of the spectrum. On top of the 3B2 feature, however, the experimental spectrum exhibits additional photo-electron peaks whose angular distribution is distinct from that for the vibronic peaks of the 3B2 state. Complete active space self-consistent field (CASSCF) method and second-order perturbation theory based on the CASSCF wave function (CASPT2) have been employed to study the lowest singlet state (1A1) of OXA. The simulation based on the results of these electronic structure calculations establishes that the overlapping peaks represent the vibrational ground level of the 1A1 state and its vibrational progression of the CO stretching mode. The 1A1 state is the lowest electronic state of OXA, and the electron affinity (EA) of OXA is 1.940 ± 0.010 eV. The 3B2 state is the first excited state with an electronic term energy of 55 ± 2 meV. The widths of the vibronic peaks of the X̃ 1A1 state are much broader than those of the ã 3B2 state, implying that the 1A1 state is indeed a transition state. The CASSCF and CASPT2 calculations suggest that the 1A1 state is at a potential maximum along the nuclear coordinate representing disrotatory motion of the two methylene groups, which leads to three-membered-ring formation, i.e., cyclopropanone. The simulation of b̃ 3B1 OXA reproduces the higher eBE portion of the spectrum very well. The term energy of the 3B1 state is 0.883 ± 0.012 eV. Photoelectron spectroscopic measurements have also been conducted for the other ion products of the O߭߫ reaction with acetone. The photoelectron imaging spectrum of the acetylcarbene (AC) radical anion exhibits a broad, structureless feature, which is assigned to the X̃ 3A′′ state of AC. The ground (2A′′) and first excited (2A′) states of the 1-methylvinoxy (1-MVO) radical have been observed in the photoelectron spectrum of the 1-MVO ion, and their vibronic structure has been analyzed. digital.library.unt.edu/ark:/67531/metadc71811/
Templated Growth of Hexagonal Nickel Carbide Nanocrystals on Vertically Aligned Carbon Nanotubes
This article discusses hexagonal nickel carbide. Nanocrystals of hexagonal nickel carbide have been synthesized via physical vapor deposition of elemental nickel onto the surface of vertically aligned carbon nanotubes. Combining high-resolution transmission electron microscopy (HRTEM) with three-dimensional atom probe tomography (3DAP) confirmed that these nanocrystals have a hexagonal structure, are enriched in carbon, and have a composition of ~Ni-25 at. % C (Ni3C). This metastable hexagonal nickel carbide phase appears to be stabilized due to the growth of the nanocrystals on the surface of the nanotubes that act as a template and also as a source of carbon. The stability of this nickel carbide phase has also been investigated by density functional theory (DFT) calculations and compared to the experimental results. digital.library.unt.edu/ark:/67531/metadc71810/
Experimental and Computational Studies of the Isomerization Reactions of Bidentate Phosphine Ligands in Triosmium Clusters: Kinetics of the Rearrangements from Bridged to Chelated Isomers and X-ray Structures of the Clusters Os3 (CO)10 (dppbz), 1,1-Os3 (CO)10 (dppbzF4), HOs3 (CO)9 [μ -1,2-PhP (C6H4-ɳ1) C6H4PPh2], and HOs3 (CO)9- [μ-1,2-PhP (C6H4-ɳ 1) C6F4PPh2]
This article discusses isomerization reactions of bidentate phosphine ligands in triosmium clusters. Abstract: The diphosphine ligand 1,2-bis(diphenylphosphino) benzene (dppbz) reacts with the activated cluster 1,2-Os3 (CO)10 (MeCN)2 (1) at room temperature to furnish a mixture of the triosmium clusters 1,2-Os3 (CO)10 (dppbz) (2) and 1,1-Os3 (CO)10 (dppbz) (3), along with a trace amount of the hydride cluster HOs3 (CO)9 [μ -1,2-PhP (C6H4-ɳ1) C6H4PPh2] (4). The dppbz-bridged cluster 2 forms as the kinetically controlled product and irreversibly transforms to the corresponding chelated isomer 3 at ambient temperature. The disposition of the dppbz ligand in 2 and 3 has been established by X-ray crystallography and 31P NMR spectroscopy, and the kinetics for the conversion 2 → 3 have been followed by UV-vis spectroscopy in toluene over the temperature range 318-343 K. The calculated activation parameters (ΔH‡ = 21.6(3)kcal/mol; ΔS‡ = -11(1)eu) and lack of CO inhibition support an intramolecular isomerization mechanism that involves the simultaneous migration of phosphine and CO groups about the cluster polyhedron. The reaction between 1 and the fluorinated diphosphine ligand 1,2-bis(diphenylphosphino) tetrafluorobenzene (dppbzF4) was examined under similar reaction conditions and was found to afford the chelated cluster 1,1-Os3 (CO)10 (dppbzF4) (6) as the sole observable product. The absence of the expected bridged isomer 1,2-Os3 (CO)10 (dppbzF4) (5) suggests that the dppbzF4 ligand destabilizes 5, thus accounting for the rapid isomerization of 5 to 6. Near-UV irradiation of clusters 3 and 6 leads to CO loss and ortho metalation of an ancillary aryl group. The resulting hydride clusters 4 and HOs3 (CO)9 [µ-1,2-PhP(C6H4-ɳ1) C6F4PPh2] (7) have been isolated and fully characterized by spectroscopic and X-ray diffraction analyses. Both 4 and 7 react with added CO under mild conditions to regenerate 3 and 6, respectively, in quantitative yield. The rearrangements of bridged to chelated diphosphine complexes in this genre of decacarbonyl clusters have been investigated by DFT calculations. The computational results support a concerted process, involving the scrambling of equatorial CO and phosphine groups via a classical merry-go-round exchange scheme. The barriers computed for this mechanism agree well with those that have been measured, and steric compression within the bridged diphosphine groups of the reactants has been calculated to reduce the barrier heights for the rearrangement. digital.library.unt.edu/ark:/67531/metadc71815/
Experimental Evidence for Heavy-Atom Tunneling in the Ring-Opening of Cyclopropylcarbinyl Radical from Intramolecular 12C/13C Kinetic Isotope Effects
This article discusses experimental evidence for heavy-atom tunneling. Abstract: The intramolecular 13C kinetic isotope effects for the ring-opening of cyclopropylcarbinyl radical were determined over a broad temperature range. The observed isotope effects are unprecedentedly large, ranging from 1.062 at 80 °C to 1.163 at -100 °C. Semiclassical calculations employing canonical variational transition-state theory drastically underpredict the observed isotope effects, but the predicted isotope effects including tunneling by a small-curvature tunneling model match well with experiment. These results and a curvature in the Arrhenius plot of the isotope effects support the recently predicted importance of heavy-atom tunneling in cyclopropylcarbinyl ring-opening. digital.library.unt.edu/ark:/67531/metadc71805/
First-Principles-Based Kinetic Monte Carlo Simulation of Nitric Oxide Reduction over Platinum Nanoparticles under Lean-Burn Conditions
This article discusses first-principles-based kinetic Monte Carlo simulation of Nitric Oxide reduction. Abstract: The kinetics for NO reduction over supported platinum under lean condition were investigated by first-principles-based kinetic Monte Carlo simulation over three-dimensional Pt nanoparticles. Model platinum nanoparticles with diameters ranging from 2.3 to 4.6 nm were constructed using a truncated octahedral cluster consisting of a two (100) facets and eight (111) facets. First-principles density functional theory (DFT) calculations were used to calculate the intrinsic kinetic parameters including the binding energies for all of the surface intermediates as well as the activation barriers and reaction energies that comprise the reaction nanoparticle. Both intra- and inter-facet diffusion of adsorbates were included to model surface diffusion effects over the particle surface. The simulation results show that under lean conditions where there is excess oxygen, NO reduction to N2 occurs solely on the (100) facets. The oxidation of NO to NO2, while much more favored on the (111) facets, can occur on both (100) and (111) facets. Only small amounts of N2O form over the (100) facets. The simulated apparent activation energies for N2 and NO2 formation over the entire particle are 45 and 42 kJ/mol, respectively. The latter is in agreement with experimentally measured value of 39 kJ/mol [Mulla, S.S., et al., Catal. Lett. 2005, 100, 267]. The effects of particle size on the activities of NO reduction to N2 and NO oxidation to NO2 depend upon the ratios of exposed surface sites. For the three-dimensional model Pt nanoparticles examined here, the fractions of the (100) terrace sites are similar while the fraction of the (111) terrace sites increases with increasing particle size. As a result, the activity for NO reduction is somewhat insensitive to the particle size which symmetrically increases the numbers of (111) and (100) facets as the size increases. NO reduction, however, increases much more dramatically when the number of the (100) sites increases over the (111) sites. NO oxidation activity, on the other hand, appears to increase with increasing particle size regardless of the symmetry or shape of the particle as the reaction occurs predominantly over the (111) sites but can also take place on the (100) terrace sites. The structure insensitivity for NO oxidation is consistent with experimental results. digital.library.unt.edu/ark:/67531/metadc71804/
Geographic Distribution of HIV/AIDS in Texas
This presentation is part of the faculty lecture series UNT Speaks Out on HIV/AIDS. This presentation discusses the geographic distribution of HIV/AIDS in Texas and the associated factors. digital.library.unt.edu/ark:/67531/metadc71783/
Input Substitution in Irrigated Agriculture in the High Plains of Texas, 1970-80
This article discusses input substitution in irrigated agriculture in the high plains of Texas. Abstract: The adaptability of irrigated agriculture in the High Plains region of Texas in the 1970-80 period is analyzed by estimating Allen partial elasticities of substitution for five key inputs (water, labor, center pivot, furrow, and wheel roll systems) used to produce two crops (cotton and grain sorghum). The results indicate that farmers have adapted to changes in a manner generally consistent with prior expectations concerning complementarity and substitutability among inputs. The output-constant price elasticity of water demand was statistically significant but relatively small (-.25). digital.library.unt.edu/ark:/67531/metadc71788/
The correlation-consistent composite approach: Application to the G3/99 test set
This article discusses the correlation-consistent composite approach. Abstract: The correlation-consistent composite approach (ccCA), an ab initio composite technique for computing atomic and molecular energies, recently has been shown to successfully reproduce experimental data for a number of systems. The ccCA is applied to the G3/99 test set, which includes 223 enthalpies of formation, 88 adiabatic ionization potentials, 58 adiabatic electron affinities, and 8 adiabatic proton affinities. Improvements on the original ccCA formalism include replacing the small basis set quadratic configuration interaction computation with a coupled cluster computation, employing a correction for scalar relativistic effects, utilizing the tight-d forms of the second-row correlation-consistent basis set extrapolation of MP2 energies, ccCA results in an almost zero mean deviation for the G3/99 set (with a best value of -0.10 kcal molˉ¹), and a 0.96 kcal molˉ¹ mean absolute deviation, which is equivalent to the accuracy of the G3X model chemistry. There are no optimized or empirical parameters included in the computation of ccCA energies. Except for a few systems to be discussed, ccCA performs as well as or better than Gn methods for most systems containing first-row atoms, while for systems containing second-row atoms, ccCA is an improvement over Gn model chemistries. digital.library.unt.edu/ark:/67531/metadc75420/
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/
The correlation consistent composite approach (ccCA): An alternative to the Gaussian-n methods
This article discusses the correlation consistent composite approach (ccCA). Abstract: An alternative to the Gaussian-n (G1, G2, and G3) composite methods of computing molecular energies is proposed and is named the "correlation consistent composite approach" (ccCA, ccCA-CBS-1, ccCA-CBS-2). This approach uses the correlation consistent polarized valence (cc-pVXZ) basis sets. The G2-1 test set of 48 enthalpies of formation (∆Hf), 38 adiabatic ionization potentials (IPs), 25 adiabatic electron affinities (EAs), and 8 adiabatic proton affinities (PAs) are computed using this approach, as well as the ∆Hf values of 30 more systems. Equilibrium molecular geometries and vibrational frequencies are obtained using B3LYP density functional theory. When applying the ccCA-CBS method with the cc-pVXZ series of basis sets augmented with diffuse functions, mean absolute deviations within the G2-1 test set compared to experiment are 1.33 kcal molˉ¹ for ∆Hf, 0.81 kcal molˉ¹ for IPs, 1.02 kcal molˉ¹ for EAs, and 1.51 kcal molˉ¹ for PAs, without including the "high-level correction" (HLC) contained in the original Gn methods. Whereas the HLC originated in the Gaussian-1 method as an isogyric correction, it evolved into a fitted parameter that minimized the error of the composite methods, eliminating its physical meaning. Recomputing the G1 and G3 enthalpies of formation without the HLC reveals a systematic trend where most ∆Hf values are significantly higher than experimental values. By extrapolating electronic energies to the complete basis set (CBS) limit and adding G3-like corrections for the core-valence and infinite-order electron correlation effects, ccCA-CBS-2 often underestimates the experimental ∆Hf, especially for larger systems. This is desired as inclusion of relativistic and atomic spin-orbit effects subsequently improves theoretical ∆Hf values to give a 0.81 kcal molˉ¹ mean absolute deviation with ccCA-CBS-2. The ccCA-CBS method is a viable "black box" method that can be used on systems with at least 10-15 heavy atoms. digital.library.unt.edu/ark:/67531/metadc75421/
Application of the Correlation Consistent Composite Approach (ccCA) to Third-Row (Ga-Kr) Molecules
This article discusses the application of the correlation consistent composite approach (ccCA). Abstract: The correlation consistent composite approach (ccCA) has been applied to the G3/05 training set of 51 energetic properties for the atoms and molecules that contain the 4p elements, Ga-Kr. When atomic and molecular first-order spin orbit coupling corrections are added to open shell atoms and molecules, the ccCA has a mean absolute deviation from experiment (MAD) of 0.95 kcal mol-1, an improvement of 0.10 kcal mol-1 over G3 and G3X model chemistries. The performance of the ccCA on third-row-containing atoms and molecules is, therefore, commensurate in accuracy with previous studies on lighter main group elements H-Ar. While the typical methods used to compute theoretical molecular spin orbit corrections may go against the spirit of "black box" model chemistries, such corrections may be necessary for molecules containing heavy elements such as Ga-Kr. For example, when second-order spin orbit corrections are added to the atomic and molecular energies, the ccCA MAD is reduced to 0.88 kcal mol-1. digital.library.unt.edu/ark:/67531/metadc75422/
Synthesis of the Five-Coordinate Ruthenium (II) Complexes [(PCP)Ru(CO)(L)][BAr'4] {PCP = 2,6-(CH2PtBu2)2 C6H3, BAr'4 = 3,5-(CF3)2C6H3, L= ɳ1-CICH2CI, ɳ 1-N2, or μ-Cl-Ru(PCP)(CO)}: Reactions with Phenyldiazomethane and Phenylacetylene
This article discusses complexes and reactions. Reaction of (PCP)Ru(CO)(CI) (1) with NaBAr'4 yields the bimetallic product [{(PCP)Ru(CO)}2 (μ-CI)][BAr'4] (2). The monomeric five-coordinate complexes [(PCP)Ru(CO)(ɳ1-CICH2CI)][BAr'4] (3) and [(PCP)Ru(CO)(ɳ1-N2)][BAr'4] (4) are synthesized upon reaction of (PCP)Ru(CO)(OTf) (6) with NaBAr'4 in CH2CI2 or C6H5F, respectively. The solid-state structures of 2,3, and 4 have been determined by X-ray diffraction studies of single crystals. The reaction of 3 with PhCHN2 or PhC=CH affords carbon-carbon coupling products involving the aryl group of the PCP ligand in transformations that likely proceed via the formation of Ru carbene or vinylidene intermediates. Density functional theory and hybrid quantum mechanics/molecular mechanics calculations were performed to investigate the bonding of weak bases to the 14-electron fragment [(PCP)Ru(CO)]+ and the energetics of different isomers of the product carbene and vinylidene complexes. digital.library.unt.edu/ark:/67531/metadc75424/
Stability Studies of Transition-Metal Linkage Isomers Using Quantum Mechanical Methods, Groups 11 and 12 Transition Metals
This article discusses stability studies of transition-metal isomers. Several hypotheses to elucidate the linkage isomer preference of the thiocyanate (SCN¯) ion have been offered. For complexes with small coordination numbers (i.e. 1 and 2) and groups 11 (Cu-triad) and 12 (Zn-triad) metals, different levels of theory and a variety of basis sets have been employed to study linkage isomerism. Similar results are obtained for all density functionals tested, pure and hybrid. Overall, good agreement, vis-á-vis experimentally identified linkage isomers, is achieved for ab initio techniques, whereas semiempirical quantum mechanical methods show a bias toward S-ligated isomers. Despite the seeming ease for the a priori prediction of the most stable thiocyanate isomers using acid/base principles, this research highlights the sensitivity of quantitative calculations of transition-metal linkage isomerism to the choice of basis set and electron correlation, particularly with post-Hartree-Fock treatments. digital.library.unt.edu/ark:/67531/metadc75419/