Practical failures from the inclusion of exact exchange: how much exact exchange is appropriate?

The influence of exact exchange incorporated into exchange—correlation functionals on the predictions of relative energies, structures, electronic states, and vibrational spectra is examined numerically. Failures of widely used hybrid exchange—correlation functionals due to either the physical unacceptability of including exact exchange or an unbalanced mixing of exact exchange are considered. One set of examples involves tetraatomic chalcogen clusters and charge transfer complexes between diatomic chalcogens and diatomic oxygen. Poor energetic predictions from Hartree-Fock rule against the inclusion of exact exchange into the exchange—correlation functionals for these systems with significant left—right electron correlation effects. The energies of the conformers of [10]annulene are considered from an unusual viewpoint, namely, the empirical adjustment of the admixture of exact exchange to match the predictions of very high level theoretical methods. For this annulene with insignificant left-right electron correlation effects, a greater (50%) percentage of exact exchange should be included. The relationship of symmetry breaking to the inclusion of exact exchange is examined for seven linear radicals, OXO (X = B, Al, Ga, In, TI). AIOS, and OAIS. exchange—correlation functionals generate symmetry adapted solutions at the expense of an unusual ordering of the Kohn-Sham orbitals, which can cause uncharacteristic electronic states, incorrect vibrational spectra, and poorer predictions of energetics. These effects are greater when exact exchange is included. In all the examples considered, the appropriate focus for a detailed discussion of molecular properties involves consideration of the effects of exact exchange.     

Neurotransmitters in the gas phase: a computational and spectroscopic study of noradrenaline

The conformational structures of noradrenaline, isolated in the gas phase, have been explored through a combination of electronic structure computation (at the B3LYP/6-31 + G?, MP2/6-31 + G?, MP2/aug-cc-pVDZ and CIS/6-31 + G? levels of theory) and mass selected ultraviolet and infrared ion dip spectroscopy (following laser ablation of the neurotransmitter into a pulsed supersonic argon expansion). Despite the many possible low-lying conformational possibilities predicted by theory, almost the entire population of jet-cooled noradrenaline adopts the global minimum structure, associated with an extended, AG1a, ethanolamine side chain conformation. Intramolecular hydrogen bonds are formed between the neighbouring hydroxyl groups on the catechol ring and between the hydroxyl and amino groups on the side chain.     

Insights into the Relationship of Catalytic Activity and Structure: A Comparison Study of Three Carbonic Anhydrase Mimics

Density functional theory (DFT) calculations were used to study the mechanism of CO₂ hydrolysis by Zn‐(1,5,9‐triazacyclododecane) and Zn‐cyclam and evaluate the associated thermodynamic and kinetic parameters. Microkinetic models were then built based on the kinetics and thermodynamics derived from first principles. Both catalysts showed very similar behavior to Zn‐cyclen, which we have reported previously, but with multiple distinctions. The intrinsic reaction rate constants for Zn‐(1,5,9‐triazacyclododecane) and Zn‐cyclam were calculated to be 2693 and 4623 M^?1 s^?1, respectively, which is in reasonable agreement with experimental values reported or estimated. The CO₂ adsorption step was found to be a rate‐limiting step for all three catalysts. Zn‐cyclam has the lowest barrier for this step due to the highest pK_a or nucleophilicity of the Zn‐OH^? form, and_, therefore, the highest intrinsic activity. However, the observed reaction rate constant also depends on the availability of the catalyst. The decrease in the observed reaction rate constant over 0–12 ms was ascribed to the decrease in the concentration of the catalytic form, Zn‐OH^?, which was primarily converted to Zn‐HCO₃^?. The reaction rate constant of Zn‐cyclam dropped much faster than those of Zn‐cyclen and Zn‐(1,5,9‐triazacyclododecane) due to lower energy of the Zn‐HCO₃^? form. The conversion of CO₂ at 1000 ms as a function of pH was calculated to compare the relative activity of these catalysts, and Zn‐cyclen was found to be the best catalyst.     

In Memoriam Vladimir Prelog (1906–1998): Some Personal Reminiscences

Some persons, by virtue of the classic status of their achievements and the lengthy duration of their careers, become legends in their own time and are often incorrectly believed to be no longer with us. As a case in point, in the early 1980s Charles Scribners Sons invited me to write an article on the American organic chemist Carl Shipp (Speed) Marvel for its Dictionary of Scientific Biography. Because one of the criteria for inclusion in DSB was that the subject be deceased, I informed the publisher that Marvel was very much alive (After Marvel had died at the age of 93 in 1988, I wrote the previously requested DSB article).     

Characterization of extracts from Papaver rhoeas and potential valorization of these extracts in dyeing applications

The aim of our work is to study the dyeing properties of extracts from natural sources such as Papaver rhoeas by modifying the conditions of the dyeing process, choosing other substrates that could be pretreated by innovative and environmentally friendly processes. The results obtained show a fairly high fixation of the extracts on the natural and artificial fibers. The use of mordants allowed the dye to be better fixed on the dyed fibers and to give several shades to the fabric. The rate of essential oil contained in Papaver rhoeas was considered important by the Clevenger process. Screening of extractive revealed the presence of polyphenols, saponins, sterols, alkaloids and flavonoids. In this study, the extractive from Papaver rhoeas was investigated as textile dyestuff.     

MODELING: A TOOL FOR ENHANCING THE SURVIVAL PROSPECTS OF AFRICAN WILDLIFE

ABSTRACT. In this article we consider the role of modeling in some aspects of the conservation of African wildlife. The first study is concerned with the endangered black rhino. Animals are being translocated from high density areas to new sites in an attempt to build up the South African population as rapidly as possible. We investigate the efficacy of different translocation strategies. Next we discuss a spatial stochastic metapopulation model used to test management strategies to enhance the survival likelihood of the rare samango monkey. The value of the model is to encourage the use of corridor policies even though there may be little apparent observable benefit in a manager's lifetime. Finally, we look at some commercial aspects of exploiting wildlife on a sustainable basis. By increasing the profitability of wildlife enterprises the incentive to conserve is increased. We look at improving the financial returns from game ranches.     

An Electrochemical Puzzle: The Catalyzed Anodic Dissolution of I-coated Palladium in Halide-Free Acid Solutions

Iodine adsorbed on a Pd electrode has been shown to catalyze the anodic dissolution of Pd in halide-free acidic solutions. An undergraduate instrumental analysis laboratory experiment has been developed that enables students to use basic electrochemical techniques (cyclic voltammetry and chronocoulometry) to detect and confirm this phenomenon. Cyclic voltammograms of clean Pd and I-coated Pd were done in 0.5 M sulfuric acid solutions containing iodide and iodine as well as halide free 0.5 M sulfuric acid. The large currents noted in the halide-free solution indicate an anodic process that is not related to the oxidation process in solutions containing iodine species. Chronocoulometry was used to determine the total charge that was passed in the 0.5 M sulfuric acid solutions for clean and I-coated Pd electrodes. The results of these experiments point to a unique catalyzed corrosion process for this otherwise inert metal.     

The Determination of Rate Constants from Known Linear Combinations of Concentrations in a Chemical Reaction

The determination of rate constants from known linear combinationsof concentrations in a chemical reaction is studied. Continuousdependence of the rate constants upon the data is demonstrated.A nonlinear least-squares method of approximation of the rateconstants is formulated and utilized in some numerical studies.