On the Fluctuation Relation for Nose-Hoover Boundary Thermostated Systems

We discuss the transient and steady state fluctuation relation for a mechanical system in contact with two deterministic thermostats at different temperatures. The system is a modified Lorentz gas in which the fixed scatterers exchange energy with the gas of particles, and the thermostats are modelled by two Nos\'e-Hoover thermostats applied at the boundaries of the system. The transient fluctuation relation, which holds only for a precise choice of the initial ensemble, is verified at all times, as expected. Times longer than the mesoscopic scale, needed for local equilibrium to be settled, are required if a different initial ensemble is considered. This shows how the transient fluctuation relation asymptotically leads to the steady state relation when, as explicitly checked in our systems, the condition found in [D.J. Searles, {\em et al.}, J. Stat. Phys. 128, 1337 (2007)], for the validity of the steady state fluctuation relation, is verified. For the steady state fluctuations of the phase space contraction rate \zL and of the dissipation function \zW, a similar relaxation regime at shorter averaging times is found. The quantity \zW satisfies with good accuracy the fluctuation relation for times larger than the mesoscopic time scale; the quantity \zL appears to begin a monotonic convergence after such times. This is consistent with the fact that \zW and \zL differ by a total time derivative, and that the tails of the probability distribution function of \zL are Gaussian.Comment: Major revision. Fig.10 was added. Version to appear in Journal of Statistical Physic

Gender and race distribution of dental graduates (1985 - 2004) and first year dental students (2000 - 2005) in South Africa

This paper, written at the close of a decade of democracy in South Africa, sets out to analyse the demographic profile of dental graduates from 1985-2004 at the five Faculties/Schools of Dentistry in South Africa. A comparison of the profiles for the pre-democracy (1985-1994) and post-apartheid (1995-2004) periods has been made. The demographic profile of first year dental students from 2000-2005 is also presented. From 1985-1994, most dental graduates were male (79%), but this changed substantially from 1995-2004, with females comprising 46% of those graduating. In the pre-democracy period, more than three-quarters of all graduates were White (78%), decreasing to 46% in the post-apartheid period under review. Black graduates increased from 6% to 24% across the two study periods. Amongst the first year dental student intake from 2000- 2005, females comprised 57%. There was an almost equal distribution across the White, Black and Asian groups. Dental faculties/schools have made important strides in transforming the demographic profile of their students. The percentage of Black graduates, however, needs to be significantly increased if it is to reflect the national population. Faculties/schools must further ensure that able students from working class background are identified and considered for acceptance into the undergraduate dental programme, and should then be offered the necessary academic and mentoring support to enable success

Enantioselective synthesis of non-proteinogenic 2-arylallyl-α-amino acids via Pd/In catalytic cascades

An efficient synthesis of both R- and S-enantiomers of 2-arylallyl-α-amino acids via a diastereoselective Pd/In mediated catalytic allylation of chiral N-sulfinyl-α-imino esters is described. The potential for further enhancement of molecular complexity and creating contiguous chiral centres by interfacing these processes with catalytic cyclisation–anion capture methodology is demonstrated

Master equation approach to the conjugate pairing rule of Lyapunov spectra for many-particle thermostatted systems

The master equation approach to Lyapunov spectra for many-particle systems is applied to non-equilibrium thermostatted systems to discuss the conjugate pairing rule. We consider iso-kinetic thermostatted systems with a shear flow sustained by an external restriction, in which particle interactions are expressed as a Gaussian white randomness. Positive Lyapunov exponents are calculated by using the Fokker-Planck equation to describe the tangent vector dynamics. We introduce another Fokker-Planck equation to describe the time-reversed tangent vector dynamics, which allows us to calculate the negative Lyapunov exponents. Using the Lyapunov exponents provided by these two Fokker-Planck equations we show the conjugate pairing rule is satisfied for thermostatted systems with a shear flow in the thermodynamic limit. We also give an explicit form to connect the Lyapunov exponents with the time-correlation of the interaction matrix in a thermostatted system with a color field.Comment: 10 page

Class and rank of differential modules

A differential module is a module equipped with a square-zero endomorphism. This structure underpins complexes of modules over rings, as well as differential graded modules over graded rings. We establish lower bounds on the class--a substitute for the length of a free complex--and on the rank of a differential module in terms of invariants of its homology. These results specialize to basic theorems in commutative algebra and algebraic topology. One instance is a common generalization of the equicharacteristic case of the New Intersection Theorem of Hochster, Peskine, P. Roberts, and Szpiro, concerning complexes over noetherian commutative rings, and of a theorem of G. Carlsson on differential graded modules over graded polynomial rings.Comment: 27 pages. Minor changes; mainly stylistic. To appear in Inventiones Mathematica

Capillary Condensation and Interface Structure of a Model Colloid-Polymer Mixture in a Porous Medium

We consider the Asakura-Oosawa model of hard sphere colloids and ideal polymers in contact with a porous matrix modeled by immobilized configurations of hard spheres. For this ternary mixture a fundamental measure density functional theory is employed, where the matrix particles are quenched and the colloids and polymers are annealed, i.e. allowed to equilibrate. We study capillary condensation of the mixture in a tiny sample of matrix as well as demixing and the fluid-fluid interface inside a bulk matrix. Density profiles normal to the interface and surface tensions are calculated and compared to the case without matrix. Two kinds of matrices are considered: (i) colloid-sized matrix particles at low packing fractions and (ii) large matrix particles at high packing fractions. These two cases show fundamentally different behavior and should both be experimentally realizable. Furthermore, we argue that capillary condensation of a colloidal suspension could be experimentally accessible. We find that in case (ii), even at high packing fractions, the main effect of the matrix is to exclude volume and, to high accuracy, the results can be mapped onto those of the same system without matrix via a simple rescaling.Comment: 12 pages, 9 figures, submitted to PR

Adsorption of Line Segments on a Square Lattice

We study the deposition of line segments on a two-dimensional square lattice. The estimates for the coverage at jamming obtained by Monte-Carlo simulations and by $7^{th}$-order time-series expansion are successfully compared. The non-trivial limit of adsorption of infinitely long segments is studied, and the lattice coverage is consistently obtained using these two approaches.Comment: 19 pages in Latex+5 postscript files sent upon request ; PTB93_

Mean Field Fluid Behavior of the Gaussian Core Model

We show that the Gaussian core model of particles interacting via a penetrable repulsive Gaussian potential, first considered by Stillinger (J. Chem. Phys. 65, 3968 (1976)), behaves like a weakly correlated ``mean field fluid'' over a surprisingly wide density and temperature range. In the bulk the structure of the fluid phase is accurately described by the random phase approximation for the direct correlation function, and by the more sophisticated HNC integral equation. The resulting pressure deviates very little from a simple, mean-field like, quadratic form in the density, while the low density virial expansion turns out to have an extremely small radius of convergence. Density profiles near a hard wall are also very accurately described by the corresponding mean-field free-energy functional. The binary version of the model exhibits a spinodal instability against de-mixing at high densities. Possible implications for semi-dilute polymer solutions are discussed.Comment: 13 pages, 2 columns, ReVTeX epsfig,multicol,amssym, 15 figures; submitted to Phys. Rev. E (change: important reference added

Nonequilibrium statistical mechanics and entropy production in a classical infinite system of rotators

We analyze the dynamics of a simple but nontrivial classical Hamiltonian system of infinitely many coupled rotators. We assume that this infinite system is driven out of thermal equilibrium either because energy is injected by an external force (Case I), or because heat flows between two thermostats at different temperatures (Case II). We discuss several possible definitions of the entropy production associated with a finite or infinite region, or with a partition of the system into a finite number of pieces. We show that these definitions satisfy the expected bounds in terms of thermostat temperatures and energy flow.Comment: 36 page

Theory of asymmetric non-additive binary hard-sphere mixtures

We show that the formal procedure of integrating out the degrees of freedom of the small spheres in a binary hard-sphere mixture works equally well for non-additive as it does for additive mixtures. For highly asymmetric mixtures (small size ratios) the resulting effective Hamiltonian of the one-component fluid of big spheres, which consists of an infinite number of many-body interactions, should be accurately approximated by truncating after the term describing the effective pair interaction. Using a density functional treatment developed originally for additive hard-sphere mixtures we determine the zero, one, and two-body contribution to the effective Hamiltonian. We demonstrate that even small degrees of positive or negative non-additivity have significant effect on the shape of the depletion potential. The second virial coefficient $B_2$, corresponding to the effective pair interaction between two big spheres, is found to be a sensitive measure of the effects of non-additivity. The variation of $B_2$ with the density of the small spheres shows significantly different behavior for additive, slightly positive and slightly negative non-additive mixtures. We discuss the possible repercussions of these results for the phase behavior of binary hard-sphere mixtures and suggest that measurements of $B_2$ might provide a means of determining the degree of non-additivity in real colloidal mixtures