Orbital measures in non-equilibrium statistical mechanics: the Onsager relations

We assume that the properties of nonequilibrium stationary states of systems of particles can be expressed in terms of weighted orbital measures, i.e. through periodic orbit expansions. This allows us to derive the Onsager relations for systems of $N$ particles subject to a Gaussian thermostat, under the assumption that the entropy production rate is equal to the phase space contraction rate. Moreover, this also allows us to prove that the relevant transport coefficients are not negative. In the appendix we give an argument for the proper way of treating grazing collisions, a source of possible singularities in the dynamics.Comment: LaTeX, 14 pages, 1 TeX figure in the tex

Gibbs entropy and irreversible thermodynamics

Recently a number of approaches has been developed to connect the microscopic dynamics of particle systems to the macroscopic properties of systems in nonequilibrium stationary states, via the theory of dynamical systems. This way a direct connection between dynamics and Irreversible Thermodynamics has been claimed to have been found. However, the main quantity used in these studies is a (coarse-grained) Gibbs entropy, which to us does not seem suitable, in its present form, to characterize nonequilibrium states. Various simplified models have also been devised to give explicit examples of how the coarse-grained approach may succeed in giving a full description of the Irreversible Thermodynamics. We analyze some of these models pointing out a number of difficulties which, in our opinion, need to be overcome in order to establish a physically relevant connection between these models and Irreversible Thermodynamics.Comment: 19 pages, 4 eps figures, LaTeX2

Thermal effects on lattice strain in hcp Fe under pressure

We compute the c/a lattice strain versus temperature for nonmagnetic hcp iron at high pressures using both first-principles linear response quasiharmonic calculations based on the full potential linear-muffin-tin-orbital (LMTO) method and the particle-in-cell (PIC) model for the vibrational partition function using a tight-binding total-energy method. The tight-binding model shows excellent agreement with the all-electron LMTO method. When hcp structure is stable, the calculated geometric mean frequency and Helmholtz free energy of hcp Fe from PIC and linear response lattice dynamics agree very well, as does the axial ratio as a function of temperature and pressure. On-site anharmonicity proves to be small up to the melting temperature, and PIC gives a good estimate of its sign and magnitude. At low pressures, hcp Fe becomes dynamically unstable at large c/a ratios, and the PIC model might fail where the structure approaches lattice instability. The PIC approximation describes well the vibrational behavior away from the instability, and thus is a reasonable approach to compute high temperature properties of materials. Our results show significant differences from earlier PIC studies, which gave much larger axial ratio increases with increasing temperature, or reported large differences between PIC and lattice dynamics results.Comment: 9 figure

First-principles thermal equation of state and thermoelasticity of hcp Fe at high pressures

We investigate the equation of state and elastic properties of hcp iron at high pressures and high temperatures using first principles linear response linear-muffin-tin-orbital method in the generalized-gradient approximation. We calculate the Helmholtz free energy as a function of volume, temperature, and volume-conserving strains, including the electronic excitation contributions from band structures and lattice vibrational contributions from quasi-harmonic lattice dynamics. We perform detailed investigations on the behavior of elastic moduli and equation of state properties as functions of temperature and pressure, including the pressure-volume equation of state, bulk modulus, the thermal expansion coefficient, the Gruneisen ratio, and the shock Hugoniot. Detailed comparison has been made with available experimental measurements and theoretical predictions.Comment: 33 pages, 12 figure

Direct Freeform Fabrication of Spatially Heterogeneous Living Cell-Impregnated Implants

The objectives of this work are the development of the processes, materials, and tooling to directly “3-D print” living, pre-seeded, patient-specific implants of spatially heterogeneous compositions. The research presented herein attempts to overcome some of the challenges to scaffolding, such as the difficulty of producing spatially heterogeneous implants that require varied seeding densities and/or cell-type distributions. In the proposed approach, living implants are fabricated by the layer-wise deposition of pre-cell-seeded alginate hydrogel. Although alginate hydrogels have been previously used to mold living implants, the properties of the alginate formulations used for molding were not suitable for 3-D printing. In addition to changing the formulation to make the alginate hydrogels “printable,” we developed a robotic hydrogel deposition system and supporting CAD software to deposit the gel in arbitrary geometries. We demonstrated this technology’s capabilities by printing alginate gel implants of multiple materials with various spatial heterogeneities, including, implants with completely embedded material clusters. The process was determined to be both viable (94±5% n=15) and sterile (less than one bacterium per 0.9 µL after 8 days of incubation). Additionally, we demonstrated the printing of a meniscus cartilage-shaped gel generated directly from a CT Scan. The proposed approach may hold advantages over other tissue printing efforts [5,9]. This technology has the potential to overcome challenges to scaffolding and could enable the efficient fabrication of spatially heterogeneous, patient-specific, living implants.Mechanical Engineerin

Note on Phase Space Contraction and Entropy Production in Thermostatted Hamiltonian Systems

The phase space contraction and the entropy production rates of Hamiltonian systems in an external field, thermostatted to obtain a stationary state are considered. While for stationary states with a constant kinetic energy the two rates are formally equal for all numbers of particles N, for stationary states with constant total (kinetic and potential) energy this only obtains for large N. However, in both cases a large number of particles is required to obtain equality with the entropy production rate of Irreversible Thermodynamics. Consequences of this for the positivity of the transport coefficients and for the Onsager relations are discussed. Numerical results are presented for the special case of the Lorentz gas.Comment: 16 pages including 1 table and 3 figures. LaTeX forma

Large Magnetic Fields and Motions of OH Masers in W75 N

We report on a second epoch of VLBA observations of the 1665 and 1667 MHz OH masers in the massive star-forming region W75 N. We find evidence to confirm the existence of very strong (~40 mG) magnetic fields near source VLA 2. The masers near VLA 2 are dynamically distinct and include a very bright spot apparently moving at 50 km/s relative to those around VLA 1. This fast-moving spot may be an example of a rare class of OH masers seen in outflows in star-forming regions. Due to the variability of these masers and the rapidity of their motions, tracking these motions will require multiple observations over a significantly shorter time baseline than obtained here. Proper motions of the masers near VLA 1 are more suggestive of streaming along magnetized shocks rather than Keplerian rotation in a disk. The motions of the easternmost cluster of masers in W75 N (B) may be tracing slow expansion around an unseen exciting source.Comment: 7 pages including 4 figures (2 color) & 3 tables, to appear in Ap

First-principles thermoelasticity of bcc iron under pressure

We investigate the elastic and isotropic aggregate properties of ferromagnetic bcc iron as a function of temperature and pressure by computing the Helmholtz free energies for the volume-conserving strained structures using the first-principles linear response linear-muffin-tin-orbital method and the generalized-gradient approximation. We include the electronic excitation contributions to the free energy from the band structures, and phonon contributions from quasi-harmonic lattice dynamics. We make detailed comparisons between our calculated elastic moduli and their temperature and pressure dependences with available experimental and theoretical data.Comment: 5 figures, 2 table

Trends in Elasticity and Electronic Structure of Transition-Metal Nitrides and Carbides from First Principles

The elastic properties of the $B_1$-structured transition-metal nitrides and their carbide counterparts are studied using the {\it ab initio\} density functional perturbation theory. The linear response results of elastic constants are in excellent agreement with those obtained from numerical derivative methods, and are also consistent with measured data. We find the following trends: (1) Bulk moduli $B$ and tetragonal shear moduli $G^{\prime}=(C_{11}-C_{12})/2$, increase and lattice constants $a_{0}$ decrease rightward or downward on the Periodic Table for the metal component or if C is replaced by N; (2) The inequality $B > G^{\prime} > G > 0$ holds for $G=C_{44}$; (3) $G$ depends strongly on the number of valence electrons per unit cell ($Z_{V}$). From the fitted curve of $G$ as a function of $Z_{V}$, we can predict that MoN is unstable in $B_{1}$ structure, and transition-metal carbonitrides ($e.g.$ ZrC$_{x}$N$_{1-x}$) and di-transition-metal carbides ($e.g.$ Hf$_{x}$Ta$_{1-x}$C) have maximum $G$ at $Z_{V} \approx 8.3$.Comment: 4 pages, 2 figures, submitted to PRL. 2 typos in ref. 15 were correcte