Onsager mechanism

A two-step process (Onsager mechanism) seems to be responsible for the photoconductivity observed in monomeric phthalocyaninatometal complexes as well as in polyphthalocyaninatogermoxanes [199b]. Electronic excitation... 

Pai DM, Enck R (1975) Onsager mechanism of photogeneration in amorphous selenium. Phys Rev B 11 5163... 

Perhaps the best starting point in a review of the nonequilibrium field, and certainly the work that most directly influenced the present theory, is Onsager s celebrated 1931 paper on the reciprocal relations [10]. This showed that the symmetry of the linear hydrodynamic transport matrix was a consequence of the time reversibility of Hamilton s equations of motion. This is an early example of the overlap between macroscopic thermodynamics and microscopic statistical mechanics. The consequences of time reversibility play an essential role in the present nonequilibrium theory, and in various fluctuation and work theorems to be discussed shortly. 

The usual emphasis on equilibrium thermodynamics is somewhat inappropriate in view of the fact that all chemical and biological processes are rate-dependent and far from equilibrium. The theory of non-equilibrium or irreversible processes is based on Onsager s reciprocity theorem. Formulation of the theory requires the introduction of concepts and parameters related to dynamically variable systems. In particular, parameters that describe a mechanism that drives the process and another parameter that follows the response of the systems. The driving parameter will be referred to as an affinity and the response as a flux. Such quantities may be defined on the premise that all action ceases once equilibrium is established. 

In the quantum mechanical continuum model, the solute is embedded in a cavity while the solvent, treated as a continuous medium having the same dielectric constant as the bulk liquid, is incorporated in the solute Hamiltonian as a perturbation. In this reaction field approach, which has its origin in Onsager s work, the bulk medium is polarized by the solute molecules and subsequently back-polarizes the solute, etc. The continuum approach has been criticized for its neglect of the molecular structure of the solvent. Also, the higher-order moments of the charge distribution, which in general are not included in the calculations, may have important effects on the results. Another important limitation of the early implementations of this method was the lack of a realistic representation of the cavity form and size in relation to the shape of the solute. 

Various treatments of these effects have been developed over a period of years. The conductance equations of Fuoss and Onsager l, based on a model of a sphere moving through a continuum, are widely used to interpret conductance data. Similar treatments n 3, as well as more rigorous statistical mechanical approaches 38>, will not be discussed here. For a comparison of these treatments see Ref. 11-38) and 39>. The Fuoss-Onsager equations are derived in Ref.36), and subsequently modified slightly by Fuoss, Onsager and Skinner in Ref. °). The forms in which these equations are commonly expressed are... 

Historically, one of the central research areas in physical chemistry has been the study of transport phenomena in electrolyte solutions. A triumph of nonequilibrium statistical mechanics has been the Debye—Hiickel—Onsager—Falkenhagen theory, where ions are treated as Brownian particles in a continuum dielectric solvent interacting through Cou-lombic forces. Because the ions are under continuous motion, the frictional force on a given ion is proportional to its velocity. The proportionality constant is the friction coefficient and has been intensely studied, both experimentally and theoretically, for almost 100... 

In the present article, we focus on the scaled particle theory as the theoretical basis for interpreting the static solution properties of liquid-crystalline polymers. It is a statistical mechanical theory originally proposed to formulate the equation of state of hard sphere fluids [11], and has been applied to obtain approximate analytical expressions for the thermodynamic quantities of solutions of hard (sphero)cylinders [12-16] or wormlike hard spherocylinders [17, 18]. Its superiority to the Onsager theory lies in that it takes higher virial terms into account, and it is distinctive from the Flory theory in that it uses no artificial lattice model. We survey this theory for wormlike hard spherocylinders in Sect. 2, and compare its predictions with typical data of various static solution properties of liquid-crystalline polymers in Sects. 3-5. As is well known, the wormlike chain (or wormlike cylinder) is a simple yet adequate model for describing dilute solution properties of stiff or semiflexible polymers. 

Reynolds (Rl, R2) was one of the earlier investigators to appreciate the random nature of turbulence. The dimensionless parameter bearing his name is widely used as a measure of the physical characteristics of steady, uniform flow. Such a measure is essentially macroscopic and does not describe the local or transient behavior at a point in the stream. In recent years much effort has been devoted to understanding the basic mechanism of momentum transport by turbulence. The early work of Prandtl (P6), Taylor (Tl), Karmdn (Kl), and Howarth (K4) laid a basis for the statistical theory of turbulence which is apparently in reasonable agreement with experiment. More recently Onsager (03), Corrsin (C6), and Kolmogoroff (K10) extended the statistical theory of turbulence to describe the available experimental data in terms of kinetic-energy... 

As for the theory of this phenomenon, it was first observed by Onsager [27a] that, since in the limit a — 0 an LCD a is expected to yield a singularity of the type —surface potential, the statistical-mechanical phase integral for counterions should diverge for a greater than some critical value, characteristic of a given valency. Indeed consider a counterion (for definiteness anion) of valency z. The appropriate phase integral is of the form... 

The nature of approximations involved in the derivation of the LPBE remains obscure (2), and after the analyses of Fowler (12), Onsager (13), and Kirkwood (14), it appears that no more can be learned about them from a statistical-mechanical argument. Following the early pronouncement of Guggenheim and Fowler (15), supported by other analysis (4), we consider the LPBE the only logical choice for a model in which the ions obey the laws of electrostatics. 

The allowance for polarization in the DH model obviates the need for separation of long-range and short-range attractive forces and for inclusion of additional repulsive interactions. Belief in the necessity to include some kind of covolume term stems from the confused analysis of Onsager (13), and is compounded by a misunderstanding of the standard state concept. Reference to a solvated standard state in which there are no interionic effects can in principle be made at any arbitrary concentration, and the only repulsive or exclusion term required is that described by the DH theory which puts limits on the ionic atmosphere size and hence on the lowering of electrical free energy. The present work therefore supports the view of Stokes (34) that the covolume term should not be included in the comparison of statistical-mechanical results with experimental ones. 

Equations (13.44) are the celebrated Onsager reciprocity relations [L. Onsager. Reciprocal relations in irreversible processes. Phys. Rev. 37, 405-26 38, 2265-79 (1931)] that relate off-diagonal Fj 7 and Ft Jj coupling and serve as a cornerstone of modem transport theory. They are derived here without reference to statistical mechanical or fluctuation assumptions. 

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