Symmetry relations in chemical kinetics arising from microscopic reversibility

It is shown that the kinetics of time-reversible chemical reactions having the same equilibrium constant but different initial conditions are closely related to one another by a directly measurable symmetry relation analogous to chemical detailed balance. In contrast to detailed balance, however, this relation does not require knowledge of the elementary steps that underlie the reaction, and remains valid in regimes where the concept of rate constants is ill-defined, such as at very short times and in the presence of low activation barriers. Numerical simulations of a model of isomerization in solution are provided to illustrate the symmetry under such conditions, and potential applications in protein folding-unfolding are pointed out.Comment: 4 pages, 1 figure, accepted to Phys Rev Let

Macroscopic proof of the Jarzynski-Wojcik fluctuation theorem for heat exchange

In a recent work, Jarzynski and Wojcik (2004 Phys. Rev. Lett. 92, 230602) have shown by using the properties of Hamiltonian dynamics and a statistical mechanical consideration that, through contact, heat exchange between two systems initially prepared at different temperatures obeys a fluctuation theorem. Here, another proof is presented, in which only macroscopic thermodynamic quantities are employed. The detailed balance condition is found to play an essential role. As a result, the theorem is found to hold under very general conditions.Comment: 9 pages, 0 figure

Tolman mass, generalized surface gravity, and entropy bounds

In any static spacetime the quasi-local Tolman mass contained within a volume can be reduced to a Gauss-like surface integral involving the flux of a suitably defined generalized surface gravity. By introducing some basic thermodynamics and invoking the Unruh effect one can then develop elementary bounds on the quasi-local entropy that are very similar in spirit to the holographic bound, and closely related to entanglement entropy.Comment: V1: 4 pages. Uses revtex4-1; V2: Three references added; V3: Some notational changes for clarity; introductory paragraph rewritten; no physics changes. This version accepted for publication in Physical Review Letter

Cosmologies with Energy Exchange

We provide a simple mathematical description of the exchange of energy between two fluids in an expanding Friedmann universe with zero spatial curvature. The evolution can be reduced to a single non-linear differential equation which we solve in physically relevant cases and provide an analysis of all the possible evolutions. Particular power-law solutions exist for the expansion scale factor and are attractors at late times under particular conditions. We show how a number of problems studied in the literature, such as cosmological vacuum energy decay, particle annihilation, and the evolution of a population of evaporating black holes, correspond to simple particular cases of our model. In all cases we can determine the effects of the energy transfer on the expansion scale factor. We also consider the situation in the presence of anti-decaying fluids and so called phantom fluids which violate the dominant energy conditions.Comment: 12 pages, 1 figur

String Gyratons in Supergravity

We study solutions of the supergravity equations with the string-like sources moving with the speed of light. An exact solution is obtained for the gravitational field of a boosted ring string in any dimension greater than three.Comment: 7 pages;v2 minor changes & references added, final in PR

Fluctuation theorem for the renormalized entropy change in the strongly nonlinear nonequilibrium regime

Generalizing a recent work [T. Taniguchi and E. G. D. Cohen, J. Stat. Phys. 126, 1 (2006)] that was based on the Onsager-Machlup theory, a nonlinear relaxation process is considered for a macroscopic thermodynamic quantity. It is found that the fluctuation theorem holds in the nonlinear nonequilibrium regime if the change of the entropy characterized by local equilibria is appropriately renormalized. The fluctuation theorem for the ordinary entropy change is recovered in the linear near-equilibrium case. This result suggests a possibility that the the information-theoretic entropy of the Shannon form may be modified in the strongly nonlinear nonequilibrium regime.Comment: 14 pages, no figures. Typos correcte

Configurational temperature control for atomic and molecular systems

A new configurational temperature thermostat suitable for molecules with holonomic constraints is derived. This thermostat has a simple set of motion equations, can generate the canonical ensemble in both position and momentum space, acts homogeneously through the spatial coordinates, and does not intrinsically violate the constraints. Our new configurational thermostat is closely related to the kinetic temperature Nosé-Hoover thermostat with feedback coupled to the position variables via a term proportional to the net molecular force. We validate the thermostat by comparing equilibrium static and dynamic quantities for a fluid of n-decane molecules under configurational and kinetic temperature control. Practical aspects concerning the implementation of the new thermostat in a molecular dynamics code and the potential applications are discussed

Planck Fluctuations, Measurement Uncertainties and the Holographic Principle

Starting from a critical analysis of recently reported surprisingly large uncertainties in length and position measurements deduced within the framework of quantum gravity, we embark on an investigation both of the correlation structure of Planck scale fluctuations and the role the holographic hypothesis is possibly playing in this context. While we prove the logical independence of the fluctuation results and the holographic hypothesis (in contrast to some recent statements in that direction) we show that by combining these two topics one can draw quite strong and interesting conclusions about the fluctuation structure and the microscopic dynamics on the Planck scale. We further argue that these findings point to a possibly new and generalized form of quantum statistical mechanics of strongly (anti)correlated systems of degrees of freedom in this fundamental regime.Comment: 19 pages, Latex, no figures, some new references, to appear ModPhysLett

Integral Constraints On cosmological Perturbations and their Energy

We show the relation between Traschen's integral equations and the energy, and ``position of the centre of mass'', of the matter perturbations in a Robertson-Walker spacetime. When the perturbations are ``localised'' we get a set of integral constraints that includes hers. We illustrate them on a simple example.Comment: 19 pages, Tex file, submitted to Classical and Quantum Gravit

Irreversible thermodynamics of open chemical networks I: Emergent cycles and broken conservation laws

In this and a companion paper we outline a general framework for the thermodynamic description of open chemical reaction networks, with special regard to metabolic networks regulating cellular physiology and biochemical functions. We first introduce closed networks "in a box", whose thermodynamics is subjected to strict physical constraints: the mass-action law, elementarity of processes, and detailed balance. We further digress on the role of solvents and on the seemingly unacknowledged property of network independence of free energy landscapes. We then open the system by assuming that the concentrations of certain substrate species (the chemostats) are fixed, whether because promptly regulated by the environment via contact with reservoirs, or because nearly constant in a time window. As a result, the system is driven out of equilibrium. A rich algebraic and topological structure ensues in the network of internal species: Emergent irreversible cycles are associated to nonvanishing affinities, whose symmetries are dictated by the breakage of conservation laws. These central results are resumed in the relation $a + b = s^Y$ between the number of fundamental affinities $a$, that of broken conservation laws $b$ and the number of chemostats $s^Y$. We decompose the steady state entropy production rate in terms of fundamental fluxes and affinities in the spirit of Schnakenberg's theory of network thermodynamics, paving the way for the forthcoming treatment of the linear regime, of efficiency and tight coupling, of free energy transduction and of thermodynamic constraints for network reconstruction.Comment: 18 page