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Characteristic State Function
The characteristic state function or Massieu's potential "Massieu's potentials ..are directly recovered as logarithms of partition functions." in statistical mechanics refers to a particular relationship between the partition function of an ensemble. In particular, if the partition function ''P'' satisfies :P = \exp(- \beta Q) \Leftrightarrow Q=-\frac \ln(P) or P = \exp(+ \beta Q) \Leftrightarrow Q=\frac \ln(P) in which ''Q'' is a thermodynamic quantity, then ''Q'' is known as the "characteristic state function" of the ensemble corresponding to "P". Beta refers to the thermodynamic beta. Examples *The microcanonical ensemble satisfies \Omega(U,V,N) = e^ \;\, hence, its characteristic state function is TS. *The canonical ensemble satisfies Z(T,V,N) = e^ \,\; hence, its characteristic state function is the Helmholtz free energy A. *The grand canonical ensemble satisfies \mathcal Z(T,V,\mu) = e^ \,\; , so its characteristic state function is the Grand potential \Phi. *The ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Statistical Mechanics
In physics, statistical mechanics is a mathematical framework that applies statistical methods and probability theory to large assemblies of microscopic entities. It does not assume or postulate any natural laws, but explains the macroscopic behavior of nature from the behavior of such ensembles. Statistical mechanics arose out of the development of classical thermodynamics, a field for which it was successful in explaining macroscopic physical properties—such as temperature, pressure, and heat capacity—in terms of microscopic parameters that fluctuate about average values and are characterized by probability distributions. This established the fields of statistical thermodynamics and statistical physics. The founding of the field of statistical mechanics is generally credited to three physicists: *Ludwig Boltzmann, who developed the fundamental interpretation of entropy in terms of a collection of microstates *James Clerk Maxwell, who developed models of probability distr ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Partition Function (statistical Mechanics)
In physics, a partition function describes the statistical properties of a system in thermodynamic equilibrium. Partition functions are functions of the thermodynamic state variables, such as the temperature and volume. Most of the aggregate thermodynamic variables of the system, such as the total energy, free energy, entropy, and pressure, can be expressed in terms of the partition function or its derivatives. The partition function is dimensionless. Each partition function is constructed to represent a particular statistical ensemble (which, in turn, corresponds to a particular free energy). The most common statistical ensembles have named partition functions. The canonical partition function applies to a canonical ensemble, in which the system is allowed to exchange heat with the environment at fixed temperature, volume, and number of particles. The grand canonical partition function applies to a grand canonical ensemble, in which the system can exchange both heat and p ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Statistical Ensemble (mathematical Physics)
In physics, specifically statistical mechanics, an ensemble (also statistical ensemble) is an idealization consisting of a large number of virtual copies (sometimes infinitely many) of a system, considered all at once, each of which represents a possible state that the real system might be in. In other words, a statistical ensemble is a set of systems of particles used in statistical mechanics to describe a single system. The concept of an ensemble was introduced by J. Willard Gibbs in 1902. A thermodynamic ensemble is a specific variety of statistical ensemble that, among other properties, is in statistical equilibrium (defined below), and is used to derive the properties of thermodynamic systems from the laws of classical or quantum mechanics. Physical considerations The ensemble formalises the notion that an experimenter repeating an experiment again and again under the same macroscopic conditions, but unable to control the microscopic details, may expect to observe a rang ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Thermodynamic Beta
In statistical thermodynamics, thermodynamic beta, also known as coldness, is the reciprocal of the thermodynamic temperature of a system:\beta = \frac (where is the temperature and is Boltzmann constant).J. Meixner (1975) "Coldness and Temperature", ''Archive for Rational Mechanics and Analysis'' 57:3, 281-29abstract It was originally introduced in 1971 (as "coldness function") by , one of the proponents of the rational thermodynamics school of thought, based on earlier proposals for a "reciprocal temperature" function.Day, W.A. and Gurtin, Morton E. (1969) "On the symmetry of the conductivity tensor and other restrictions in the nonlinear theory of heat conduction", ''Archive for Rational Mechanics and Analysis'' 33:1, 26-32 (Springer-Verlag)abstractJ. Castle, W. Emmenish, R. Henkes, R. Miller, and J. Rayne (1965) Science by Degrees: ''Temperature from Zero to Zero'' (Westinghouse Search Book Series, Walker and Company, New York). Thermodynamic beta has units reciprocal to ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Microcanonical Ensemble
In statistical mechanics, the microcanonical ensemble is a statistical ensemble that represents the possible states of a mechanical system whose total energy is exactly specified. The system is assumed to be isolated in the sense that it cannot exchange energy or particles with its environment, so that (by conservation of energy) the energy of the system does not change with time. The primary macroscopic variables of the microcanonical ensemble are the total number of particles in the system (symbol: ), the system's volume (symbol: ), as well as the total energy in the system (symbol: ). Each of these is assumed to be constant in the ensemble. For this reason, the microcanonical ensemble is sometimes called the ensemble. In simple terms, the microcanonical ensemble is defined by assigning an equal probability to every microstate whose energy falls within a range centered at . All other microstates are given a probability of zero. Since the probabilities must add up to 1, the ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Canonical Ensemble
In statistical mechanics, a canonical ensemble is the statistical ensemble that represents the possible states of a mechanical system in thermal equilibrium with a heat bath at a fixed temperature. The system can exchange energy with the heat bath, so that the states of the system will differ in total energy. The principal thermodynamic variable of the canonical ensemble, determining the probability distribution of states, is the absolute temperature (symbol: ). The ensemble typically also depends on mechanical variables such as the number of particles in the system (symbol: ) and the system's volume (symbol: ), each of which influence the nature of the system's internal states. An ensemble with these three parameters is sometimes called the ensemble. The canonical ensemble assigns a probability to each distinct microstate given by the following exponential: :P = e^, where is the total energy of the microstate, and is the Boltzmann constant. The number is the free ener ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Helmholtz Free Energy
In thermodynamics, the Helmholtz free energy (or Helmholtz energy) is a thermodynamic potential that measures the useful work obtainable from a closed thermodynamic system at a constant temperature (isothermal In thermodynamics, an isothermal process is a type of thermodynamic process in which the temperature ''T'' of a system remains constant: Δ''T'' = 0. This typically occurs when a system is in contact with an outside thermal reservoir, and ...). The change in the Helmholtz energy during a process is equal to the maximum amount of work that the system can perform in a thermodynamic process in which temperature is held constant. At constant temperature, the Helmholtz free energy is minimized at equilibrium. In contrast, the Gibbs free energy or free enthalpy is most commonly used as a measure of thermodynamic potential (especially in chemistry) when it is convenient for applications that occur at constant ''pressure''. For example, in explosives research Helmholtz ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Grand Canonical Ensemble
In statistical mechanics, the grand canonical ensemble (also known as the macrocanonical ensemble) is the statistical ensemble that is used to represent the possible states of a mechanical system of particles that are in thermodynamic equilibrium (thermal and chemical) with a reservoir. The system is said to be open in the sense that the system can exchange energy and particles with a reservoir, so that various possible states of the system can differ in both their total energy and total number of particles. The system's volume, shape, and other external coordinates are kept the same in all possible states of the system. The thermodynamic variables of the grand canonical ensemble are chemical potential (symbol: ) and absolute temperature (symbol: . The ensemble is also dependent on mechanical variables such as volume (symbol: which influence the nature of the system's internal states. This ensemble is therefore sometimes called the ensemble, as each of these three quantities ar ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Grand Potential
The grand potential is a quantity used in statistical mechanics, especially for irreversible processes in open systems. The grand potential is the characteristic state function for the grand canonical ensemble. Definition Grand potential is defined by : \Phi_ \ \stackrel\ U - T S - \mu N where ''U'' is the internal energy, ''T'' is the temperature of the system, ''S'' is the entropy, μ is the chemical potential, and ''N'' is the number of particles in the system. The change in the grand potential is given by : \begin d\Phi_ & = dU - TdS - SdT - \mu dN - Nd\mu \\ & = - P dV - S dT - N d\mu \end where ''P'' is pressure and ''V'' is volume, using the fundamental thermodynamic relation (combined first and second thermodynamic laws); :dU = TdS - PdV + \mu dN When the system is in thermodynamic equilibrium, ΦG is a minimum. This can be seen by considering that dΦG is zero if the volume is fixed and the temperature and chemical potential have stopped evolving. Landau free ene ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Gibbs Free Energy
In thermodynamics, the Gibbs free energy (or Gibbs energy; symbol G) is a thermodynamic potential that can be used to calculate the maximum amount of work that may be performed by a thermodynamically closed system at constant temperature and pressure. It also provides a necessary condition for processes such as chemical reactions that may occur under these conditions. The Gibbs free energy change , measured in joules in SI) is the ''maximum'' amount of non-expansion work that can be extracted from a closed system (one that can exchange heat and work with its surroundings, but not matter) at fixed temperature and pressure. This maximum can be attained only in a completely reversible process. When a system transforms reversibly from an initial state to a final state under these conditions, the decrease in Gibbs free energy equals the work done by the system to its surroundings, minus the work of the pressure forces. The Gibbs energy is the thermodynamic potential that is minim ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
