Use of cluster expansion techniques in quantum chemistry. A linear response model for calculating energy differences

In this paper we have reviewed the theoretical framework of the coupled-cluster (cc) based linear response model as a tool for directly calculating energy differences of spectroscopic interest like excitation energy (ee), ionisation potential (ip) or electron affinity (ea). In this model, the ground state of a many-electron system is described as in a coupled cluster theory for closed shells. The electronic ground state is supposed to interact with an external photon field of frequencyw, and the poles of the linear response function as a function ofw furnish with the elementary excitations of the system. Depending on the general form of the coupling term chosen, appropriate difference energies like ee, ip or EA may be generated. Pertinent derivations of the general working equations are reviewed, and specific details as well as approximations for ee, ip or ea are indicated. It is shown that the theory bears a close resemblance to the equation of motion (eom) method but is superior to the latter in that the ground state correlation is taken to all orders and may be looked upon as essentially a variant of renormalisedtda. A perturbative analysis elucidating the underlying perturbative structure of the formulation is also given which reveals that the theory has a hybrid structure: the correlation terms are treated akin to an open shellmbpt, while the relaxation terms are treated akin to a Green function theory. A critique of the methodvis-a-vis other cc-based approaches for difference energies forms the concluding part of our review.     

The role of various binding materials for trace elemental analysis of powder samples using laser-induced breakdown spectroscopy

Study of various binding materials like potassium bromide, poly(vinyl alcohol), starch, silver and aluminum has been carried out using laser-induced breakdown spectroscopy (LIBS). The role of matrix effects using these five binders on LIBS signal intensity was investigated for better performance of LIBS technique as a quantitative analytical tool. For comparative study of different binders, the signal intensity of different Mg lines at 518.3, 517.2, 383.8 and 279.5 nm wavelengths were recorded for pellets prepared with known concentrations of Mg in these binders. The influence of laser energy on ablated mass under different binding materials and its correlation with LIBS signal intensity has been explored. Optical scanning microscopy images of the ablated crater were studied to understand the laser ablation process. The study revealed that the binding material plays an important role in the generation of LIBS signal. The relative signal intensity measured for a standard Mg line (at 518.3 nm) were 735, 538, 387, 227 and 130 for potassium bromide, starch, poly(vinyl alcohol), silver and aluminum as binders, respectively. This indicates clearly that potassium bromide is better as a binder for LIBS studies of powder samples.     

Effect of Enzyme Modification of Corn Grits on their Properties as an Adsorbent in a Skarstrom Pressure Swing Cycle Dryer

Corn grits have been tested as a desiccant in a pressure swing adsorption (PSA) system to produce dry air. Two sizes of unmodified corn grits were tested in the PSA system: 2.16 and 0.978 mm in diameter, which dried moist air to dew points of –42°C and –69°C, respectively. A modification technology has been developed for the corn grits that gives an increase in the operational adsorptive capacity in a pressure swing adsorption system, so that they remove as much moisture from air as molecular sieves at the same conditions. After modification, 2.16 mm corn grits dry moist air to a –56°C dew point and the 0.978 mm corn grits dry air to a –80°C dew point. The modification process creates surface modifications on the corn grits apparently making more adsorption sites easily available. The modification procedure increases the specific surface area of the grits and possibly decreases the crystallinity, which would make more hydroxyl groups available for adsorption of water. Possible applications of using corn grits in the pressure swing adsorption system include industrial gas dryers, sorptive cooling air conditioners, and recycling equipment for industrial solvents.     

Theory of measurement of gas-adsorption equilibria by rotational oscillations

The gas adsorbed on the inner surface of a highly porous material like activated carbon or zeolite can be measured by slow damped oscillations of a torsional pendulum. The physical principles and the theory of this method are outlined. Formulas are given relating the increase in mass due to adsorption to changes of the frequency and the logarithmic decrement of slow, damped rotational oscillations of the pendulum. Preliminary measurements of gas adsorption equilibria of nitrogen on activated carbon show that the ratio of the mass adsorbedm, to the mass of the adsorbentm ^s , can be determined by this method with mean absolute error |m/m ^s |0.04%.Dedicated to the memory of Joseph Kestin (1913–1993).     

Measurement of Diffusion in Zeolites—A Never Ending Challenge?

A review is given on the main problems associated with the determination and interpretation of molecular diffusion in zeolites. It is shown that the diffusivities may most decisively depend on the relevant space and time scales of observation, as well as on the physical state under which the measurements are carried out. Special emphasis is given to the microscopic techniques and their most recent evidence on the existence of transport resistances distributed over the intracrystalline space.     

Molecular and nanoscale materials and devices in electronics

Over the past several years, there have been many significant advances toward the realization of electronic computers integrated on the molecular scale and a much greater understanding of the types of materials that will be useful in molecular devices and their properties. It was demonstrated that individual molecules could serve as incomprehensibly tiny switch and wire one million times smaller than those on conventional silicon microchip. This has resulted very recently in the assembly and demonstration of tiny computer logic circuits built from such molecular scale devices. The purpose of this review is to provide a general introduction to molecular and nanoscale materials and devices in electronics.     

Characteristics and production of thermostable α-amylase

Thermostable α-amylases have application in a variety of industrial processes and enzymes from a substantial number of thermophilic bacteria and fungi have been screened and characterized to varying degrees. The characteristics of these enzymes are summarized in this review. The genetics of α-amylase production inBacillus subtilis is reviewed and classical and recombinant DNA approaches to increasing α-amylase production are discussed.     

Theoretical study of the effect of frit quality on chromatography using computational fluid dynamics

Summary Frits at both ends of a chromatographic column, especially for a preparative column, have significant influence on the flow distribution within the column and thus the column efficiency. However, frits have received little attention from chromatographers in the past. Here a theoretical study was conducted with the aid of CFD software FLUENT to investigate the effect of frits on the performance of homogeneous and heterogeneous chromatographic columns. A dimensionless number,FQ, was applied to characterize frit quality. This study visualized how frit quality affects the flow distribution and the concentration band, the shape of eluted pulse at the colum exit and column efficiency. Simulation results show that the development length of the flow distribution is related toFQ but has nothing to do with the packing heterogeneity. The curvature of the concentration band in a column depends onFQ and packing quality. This study shows column efficiency can be improved significantly by increasingFQ and/or frit permeability.     

New approaches in radical carbonylation chemistry: fluorous applications and designed tandem processes by species-hybridization with anions and transition metal species

New approaches in radical carbonylation chemistry are described. We have successfully integrated tin mediated radical carbonylation chemistry into modern fluorous applications and separation techniques. We revealed that radical carbonylation reactions can be performed using fluorous tin mediators, such as fluorous tin hydride and fluorous allyltin reagents. Fine tuning of the reaction conditions resulted in a good efficiency equivalent to conventional tin mediators. The tedious procedure of removing organotin byproducts can be circumvented through the use of fluorous/organic liquid-liquid extraction or fluorous liquid-solid phase extraction with fluorous reverse phase silica (FRPS). Also described are newly developed tandem carbonylation reactions that are based on species hybridization approaches. Using a radical/anionic hybrid system based on zinc-induced one-electron reduction, we achieved a three-component coupling reaction consisting of 4-alkenyl iodides, carbon monoxide, and electron-deficient alkenes. We observed two types of annulations processes, namely [4 + 1](radical)/[3 + 2](anionic) and [5 + 1](radical)/[3 + 2](anionic), which lead to the production of bicyclo[3.3.0]octanols and bicyclo[3.2.1]octanols, respectively. We found a radical/palladium hybrid system to be useful in the construction of new cyclic systems that incorporate two or three molecules of carbon monoxide.