High-pressure adsorption of supercritical gases on activated carbons: An improved approach based on the density functional theory and the bender equation of state

Adsorption of nitrogen, argon, methane, and carbon dioxide on activated carbon Norit R1 over a wide range of pressure (up to 50 MPa) at temperatures from 298 to 343 K (supercritical conditions) is analyzed by means of the density functional theory modified by incorporating the Bender equation of state, which describes the bulk phase properties with very high accuracy. It has allowed us to precisely describe the experimental data of carbon dioxide adsorption slightly above and below its critical temperatures. The pore size distribution (PSD) obtained with supercritical gases at ambient temperatures compares reasonably well with the PSD obtained with subcritical nitrogen at 77 K. Our approach does not require the skeletal density of activated carbon from helium adsorption measurements to calculate excess adsorption. Instead, this density is treated as a fitting parameter, and in all cases its values are found to fall into a very narrow range close to 2000 kg/m(3). It was shown that in the case of high-pressure adsorption of supercritical gases the PSD could be reliably obtained for the range of pore width between 0.6 and 3 run. All wider pores can be reliably characterized only in terms of surface area as their corresponding excess local isotherms are the same over a practical range of pressure.

Martensite Crystallography - the apparent controversy between the infinitesimal deformation approach and the phenomenological theory of martensitic transformations

The aim of this article is to demonstrate that the apparent controversy between the infinitesimal deformation (ID) approach and the phenomenological theory of martensitic transformations (PTMTs) in predicting the crystallographic characteristics of a martensitic transformation is entirely based on unjustified approximations associated with the way in which the ID calculations are performed. When applied correctly, the ID approach is shown to be absolutely identical to the PTMT. Nevertheless, there may be some advantages in using the ID approach. In particular, it is somewhat simpler than the PTMT; it is based on a physical concept that is easier to understand and, most important, it may provide a tool for investigating some of the features of martensitic transformations that have eluded explanation via the PTMT.

Tractable molecular theory of transport of Lennard-Jones fluids in nanopores

We present here a tractable theory of transport of simple fluids in cylindrical nanopores, which is applicable over a wide range of densities and pore sizes. In the Henry law low-density region the theory considers the trajectories of molecules oscillating between diffuse wall collisions, while at higher densities beyond this region the contribution from viscous flow becomes significant and is included through our recent approach utilizing a local average density model. The model is validated by means of equilibrium as well nonequilibrium molecular dynamics simulations of supercritical methane transport in cylindrical silica pores over a wide range of temperature, density, and pore size. The model for the Henry law region is exact and found to yield an excellent match with simulations at all conditions, including the single-file region of very small pore size where it is shown to provide the density-independent collective transport coefficient. It is also shown that in the absence of dispersive interactions the model reduces to the classical Knudsen result, but in the presence of such interactions the latter model drastically overpredicts the transport coefficient. For larger micropores beyond the single-file region the transport coefficient is reduced at high density because of intermolecular interactions and hindrance to particle crossings leading to a large decrease in surface slip that is not well represented by the model. However, for mesopores the transport coefficient increases monotonically with density, over the range studied, and is very well predicted by the theory, though at very high density the contribution from surface slip is slightly overpredicted. It is also seen that the concept of activated diffusion, commonly associated with diffusion in small pores, is fundamentally invalid for smooth pores, and the apparent activation energy is not simply related to the minimum pore potential or the adsorption energy as generally assumed. (C) 2004 American Institute of Physics.

On bridging the gap: The relevance of theory to the practice of conflict resolution

It is often claimed that policy makers and scholars inhabit different worlds and have little for each other. We challenge this perception and claim that there is a strong symbiotic relationship between the two. This relationship is particularly strong in the field of conflict where policy makers may be in desperate need of guidelines, advice and analysis on how to transform complex conflict situations into more peaceful ones. We suggest that policy makers may think in terms of macro and micro-level theories and ideas if they wish to embrace better strategies of conflict resolution.

Theory of strongly correlated electron systems. I. Intersite coulomb interaction and the approximation of renormalized fermions in total energy calculations

The diagrammatic strong-coupling perturbation theory (SCPT) for correlated electron systems is developed for intersite Coulomb interaction and for a nonorthogonal basis set. The construction is based on iterations of exact closed equations for many - electron Green functions (GFs) for Hubbard operators in terms of functional derivatives with respect to external sources. The graphs, which do not contain the contributions from the fluctuations of the local population numbers of the ion states, play a special role: a one-to-one correspondence is found between the subset of such graphs for the many - electron GFs and the complete set of Feynman graphs of weak-coupling perturbation theory (WCPT) for single-electron GFs. This fact is used for formulation of the approximation of renormalized Fermions (ARF) in which the many-electron quasi-particles behave analogously to normal Fermions. Then, by analyzing: (a) Sham's equation, which connects the self-energy and the exchange- correlation potential in density functional theory (DFT); and (b) the Galitskii and Migdal expressions for the total energy, written within WCPT and within ARF SCPT, a way we suggest a method to improve the description of the systems with correlated electrons within the local density approximation (LDA) to DFT. The formulation, in terms of renormalized Fermions LIDA (RF LDA), is obtained by introducing the spectral weights of the many electron GFs into the definitions of the charge density, the overlap matrices, effective mixing and hopping matrix elements, into existing electronic structure codes, whereas the weights themselves have to be found from an additional set of equations. Compared with LDA+U and self-interaction correction (SIC) methods, RF LDA has the advantage of taking into account the transfer of spectral weights, and, when formulated in terms of GFs, also allows for consideration of excitations and nonzero temperature. Going beyond the ARF SCPT, as well as RF LIDA, and taking into account the fluctuations of ion population numbers would require writing completely new codes for ab initio calculations. The application of RF LDA for ab initio band structure calculations for rare earth metals is presented in part 11 of this study (this issue). (c) 2005 Wiley Periodicals, Inc.

The chemical composition of α cen A: Strong lines and the ABO theory of collisional line broadening

The mean abundances of Mg, Si, Ca, Ti, Cr, and Fe based on both strong and weak lines of alpha CenAare determined by matching the observed line profiles with those synthesised from stellar atmospheric models and comparing these results with a similar analysis for the Sun. There is good agreement between the abundances from strong and weak lines. Strong lines should generally be an excellent indicator of abundance and far easier to measure than the weak lines normally used. Until the development of the Anstee, Barklem, and O'Mara ( ABO) theory for collisional line broadening, the uncertainty in the value of the damping constant prevented strong lines being used for abundance determinations other than in close differential analyses. We found that alpha Cen A has a mean overabundance of 0.12 +/- 0.06 dex compared to solar mean abundances. This result agrees remarkably well with previous studies that did not use strong lines or the ABO theory for collisional line broadening. Our result supports the conclusion that reliable abundances can be derived from strong lines provided this new theory for line broadening is used to calculate the van derWaals damping.

Imaginary relish and exquisite torture: The elaborated intrusion theory of desire

The authors argue that human desire involves conscious cognition that has strong affective connotation and is potentially involved in the determination of appetitive behavior rather than being epiphenomenal to it. Intrusive thoughts about appetitive targets are triggered automatically by external or physiological cues and by cognitive associates. When intrusions elicit significant pleasure or relief, cognitive elaboration usually ensues. Elaboration competes with concurrent cognitive tasks through retrieval of target-related information and its retention in working memory. Sensory images are especially important products of intrusion and elaboration because they simulate the sensory and emotional qualities of target acquisition. Desire images are momentarily rewarding but amplify awareness of somatic and emotional deficits. Effects of desires on behavior are moderated by competing incentives, target availability, and skills. The theory provides a coherent account of existing data and suggests new directions for research and treatment.