Boltzmann equilibrium relation

In the second equality we have used Eq. (1.245). The densities rt+/ (x) are related to their bulk value by the Boltzmann equilibrium relations... 

At this point, one simply remarks that at long times (t >r") the relation (4.155) yields the Boltzmann equilibrium distribution. 

Fig. 17 Energy as a function of a T-T distance and b T-T-T angle used in the simulation procedure (calculated as smoothing spline fits to Boltzmann equilibrium interpretations of the histogrammed data taken from 32 representative zeolite crystal structures). Only the central portions are shown, c The contribution to the energy sum for the merging of two symmetry-related atoms merging is only permitted when the two atoms are at less than a defined minimum distance [84], Reproduced with the kind permission of the Nature Publishing Group (http //www.nature.com/)...

To obtain relations between carrier density at the interface and at the inner edge of the depletion layer (the thickness of the space charge layer dsc is defined by Eq. (22)), we assume Boltzmann equilibrium for the carriers across the space charge layer. Using Eqs. (3a) and (3b), we have... 

In Section II we will review thermodynamics and the fluctuation-dissipation theorem for excess heat production based on the Boltzmann equilibrium distribution. We will also mention the nonequilibrium work relation by Jarzynski. In Section III, we will extend the fluctuation-dissipation theorem for the superstatisitcal equilibrium distribution. The fluctuation-dissipation theorem can be written as a superposition of correlation functions with different temperatures. When the decay constant of a correlation function depends on temperature, we can expect various behaviors in the excess heat. In Section IV, we will consider the case of the microcanonical equilibrium distribution. We will numerically show the breaking of nonergodic adiabatic invariant in the mixed phase space. In the last section, we will conclude and comment. 

Rapid (non-radiative) internal conversion leads to the lowest vibronic excitation level of the Si manifold. Subsequent transition from this level to one of the vibronic excitation levels of the So manifold is radiative and corresponds to either spontaneous or stimulated emission, SE. In terms of a simple model, stimulated emission is generated through the interaction of the excited molecules with other photons of equal energy. This process can only become important with, respect to other competitive processes, such as spontaneous emission, when the concentration of excited states is very high, i.e. when the population of the upper state exceeds that of the lower state, a situation denoted by the term population inversion. In other words, the Boltzmann equilibrium of states must be disturbed. Notably, the lasing transition relates to energy levels that are not directly involved in the optical pumping process. The laser potential of an active material is characterized by Eq. (6-3). 

Boltzmann Equation. The equation which relates the composition of equilibrium mixtures to relative thermochemical stabilities and temperature. 

The quantities n, V, and (3 /m) T are thus the first five (velocity) moments of the distribution function. In the above equation, k is the Boltzmann constant the definition of temperature relates the kinetic energy associated with the random motion of the particles to kT for each degree of freedom. If an equation of state is derived using this equilibrium distribution function, by determining the pressure in the gas (see Section 1.11), then this kinetic theory definition of the temperature is seen to be the absolute temperature that appears in the ideal gas law. 

When nuclei with spin are placed in a magnetic field, they distribute themselves between two Zeeman energy states. At thermal equilibrium the number (N) of nuclei in the upper (a) and lower (j8) states are related by the Boltzmann equation (1) where AE=E — Ep is the energy difference between the states. In a magnetic field (Hq), E = yhHo and... 

Similar convection-diffusion equations to the Navier-Stokes equation can be formulated for enthalpy or species concentration. In all of these formulations there is always a superposition of diffusive and convective transport of a field quantity, supplemented by source terms describing creation or destruction of the transported quantity. There are two fundamental assumptions on which the Navier-Stokes and other convection-diffusion equations are based. The first and most fundamental is the continuum hypothesis it is assumed that the fluid can be described by a scalar or vector field, such as density or velocity. In fact, the field quantities have to be regarded as local averages over a large number of particles contained in a volume element embracing the point of interest. The second hypothesis relates to the local statistical distribution of the particles in phase space the standard convection-diffusion equations rely on the assumption of local thermal equilibrium. For gas flow, this means that a Maxwell-Boltzmann distribution is assumed for the velocity of the particles in the frame-of-reference co-moving with the fluid. Especially the second assumption may break dovm when gas flow at high temperature or low pressure in micro channels is considered, as will be discussed below. 

This equation is called the Curie law and relates the equilibrium magnetization M0 to the strength of the magnetic field B0. The constants have the following meaning I is the nuclear spin quantum number (see below), y is the gyromagnetic ratio specific for a given isotope, h is Planck s constant, kB is Boltzmann s constant, N is the number of nuclei and T is the temperature. 

Two remaining problems relating to the treatment of solvation include the slowness of Poisson-Boltzmann calculations, when these are used to treat electrostatic effects, and the difficulty of keeping buried, explicit solvent in equilibrium with the external solvent when, e.g., there are changes in nearby solute groups in an alchemical simulation. Faster methods for solving the Poisson-Boltzmann equation by means of parallel finite element techniques are becoming available, however.22 24... 

Twenty years ago, Bogolubov3 developed a method of generalizing the Boltzmann equation for moderately dense gases. His idea was that if one starts with a gas in a given initial state, its evolution is at first determined by the initial conditions. After a lapse of time—of the order of several collision times—the system reaches a state of quasi-equilibrium which does not depend on the initial conditions and in which the w-particle distribution functions (n > 2) depend on the time only through the one-particle distribution function. With these simple statements Bogolubov derived a Boltzmann equation taking into account delocalization effects due to the finite radius of the particles, and he also established the formal relations that the n-particle distribution function has to obey. 

Infrared spectroscopy 100-1500 Intensity 1 of rotational lines of light molecules Boltzmann factor for rotational levels related to I Also Doppler line broadening useful, principal applications to plasmas and astrophysical observations, proper sampling, lack of equilibrium, atmospheric absorption often problems... 

It is most remarkable that the entropy production in a nonequilibrium steady state is directly related to the time asymmetry in the dynamical randomness of nonequilibrium fluctuations. The entropy production turns out to be the difference in the amounts of temporal disorder between the backward and forward paths or histories. In nonequilibrium steady states, the temporal disorder of the time reversals is larger than the temporal disorder h of the paths themselves. This is expressed by the principle of temporal ordering, according to which the typical paths are more ordered than their corresponding time reversals in nonequilibrium steady states. This principle is proved with nonequilibrium statistical mechanics and is a corollary of the second law of thermodynamics. Temporal ordering is possible out of equilibrium because of the increase of spatial disorder. There is thus no contradiction with Boltzmann s interpretation of the second law. Contrary to Boltzmann s interpretation, which deals with disorder in space at a fixed time, the principle of temporal ordering is concerned by order or disorder along the time axis, in the sequence of pictures of the nonequilibrium process filmed as a movie. The emphasis of the dynamical aspects is a recent trend that finds its roots in Shannon s information theory and modem dynamical systems theory. This can explain why we had to wait the last decade before these dynamical aspects of the second law were discovered. 

This introduces a new unknown (and free at this stage) coefficient K. In the case of a system of molecules in a thermal bath (definitely not the one we consider), there is a relation between D and K such that, at thermal equilibrium, the equilibrium density in the potential (h is given by Boltzmann s law. This requires that K = mD/hgT, where kg is Boltzmann s constant and T the absolute temperature. In Eq. (12) the factor p in front of in is to ensure that, if... 

If we are going to relate the properties of our system to a physical situation, we need to be able to characterize the system s temperature, T. In a macroscopic collection of atoms that is in equilibrium at temperature T, the velocities of the atoms are distributed according to the Maxwell -Boltzmann distribution. One of the key properties of this distribution is that the average kinetic energy of each degree of freedom is... 

Here the pre-exponential factor At is the product of a temperature-dependent constant (ksT/h) = 2 X 10 °Ts where ke and h are the Boltzmann and Planck constants, and a solvent-specific coefficient that relates to both the solvent viscosity and to its orientational relaxation rate. This coefficient may be near unity for very mobile solvent molecules but may be considerably less than unity for viscous or orientationally hindered highly stractured solvents. The exponential factor involves the activation Gibbs energy that describes the height of the barrier to the formation of the activated complex from the reactants. It also describes temperature and pressure dependencies of the reaction rate. It is assumed that the activated complex is in equilibrium with the reactants, but that its change to form the products is rapid and independent of its environment in the solution (de Sainte Claire et al., 1997). 

Kinetic experiments, while useful in estimating the adatom cohesive energy of a cluster, become very complicated if pair energies at more than one bond state, or information on the inter-adatom potential, are desirable. The distance dependence of pair interaction can be more easily derived by an equilibrium experiment.173 The principle is very simple. At equilibrium, the relative frequencies of observing the two adatoms at various bond states or bond separations at a given temperature are related to their pair energies according to the Boltzmann factors. Thus... 

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