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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 ...
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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 ...
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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 ...
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Planck's Law
In physics, Planck's law describes the spectral density of electromagnetic radiation emitted by a black body in thermal equilibrium at a given temperature , when there is no net flow of matter or energy between the body and its environment. At the end of the 19th century, physicists were unable to explain why the observed spectrum of black-body radiation, which by then had been accurately measured, diverged significantly at higher frequencies from that predicted by existing theories. In 1900, German physicist Max Planck heuristically derived a formula for the observed spectrum by assuming that a hypothetical electrically charged oscillator in a cavity that contained black-body radiation could only change its energy in a minimal increment, , that was proportional to the frequency of its associated electromagnetic wave. This resolved the problem of the ultraviolet catastrophe predicted by classical physics. This discovery was a pioneering insight of modern physics and is of fundam ...
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Maxwell Speed Distribution
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Maxwell–Boltzmann Statistics
In statistical mechanics, Maxwell–Boltzmann statistics describes the distribution of Classical physics, classical material particles over various energy states in thermal equilibrium. It is applicable when the temperature is high enough or the particle density is low enough to render quantum effects negligible. The expected number of particles with energy \varepsilon_i for Maxwell–Boltzmann statistics is :\langle N_i \rangle = \frac = \frac\,g_i e^, where: *\varepsilon_i is the energy of the ''i''-th energy level, *\langle N_i \rangle is the average number of particles in the set of states with energy \varepsilon_i, *g_i is the Degenerate energy level, degeneracy of energy level ''i'', that is, the number of states with energy \varepsilon_i which may nevertheless be distinguished from each other by some other means,For example, two simple point particles may have the same energy, but different momentum vectors. They may be distinguished from each other on this basis, and th ...
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Boltzmann Distribution
In statistical mechanics and mathematics, a Boltzmann distribution (also called Gibbs distribution Translated by J.B. Sykes and M.J. Kearsley. See section 28) is a probability distribution or probability measure that gives the probability that a system will be in a certain state as a function of that state's energy and the temperature of the system. The distribution is expressed in the form: :p_i \propto e^ where is the probability of the system being in state , is the energy of that state, and a constant of the distribution is the product of the Boltzmann constant and thermodynamic temperature . The symbol \propto denotes proportionality (see for the proportionality constant). The term ''system'' here has a very wide meaning; it can range from a collection of 'sufficient number' of atoms or a single atom to a macroscopic system such as a natural gas storage tank. Therefore the Boltzmann distribution can be used to solve a very wide variety of problems. The distribu ...
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Variance
In probability theory and statistics, variance is the expectation of the squared deviation of a random variable from its population mean or sample mean. Variance is a measure of dispersion, meaning it is a measure of how far a set of numbers is spread out from their average value. Variance has a central role in statistics, where some ideas that use it include descriptive statistics, statistical inference, hypothesis testing, goodness of fit, and Monte Carlo sampling. Variance is an important tool in the sciences, where statistical analysis of data is common. The variance is the square of the standard deviation, the second central moment of a distribution, and the covariance of the random variable with itself, and it is often represented by \sigma^2, s^2, \operatorname(X), V(X), or \mathbb(X). An advantage of variance as a measure of dispersion is that it is more amenable to algebraic manipulation than other measures of dispersion such as the expected absolute deviation; for e ...
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Thermal Fluctuations
In statistical mechanics, thermal fluctuations are random deviations of a system from its average state, that occur in a system at equilibrium.In statistical mechanics they are often simply referred to as fluctuations. All thermal fluctuations become larger and more frequent as the temperature increases, and likewise they decrease as temperature approaches absolute zero. Thermal fluctuations are a basic manifestation of the temperature of systems: A system at nonzero temperature does not stay in its equilibrium microscopic state, but instead randomly samples all possible states, with probabilities given by the Boltzmann distribution. Thermal fluctuations generally affect all the degrees of freedom of a system: There can be random vibrations (phonons), random rotations ( rotons), random electronic excitations, and so forth. Thermodynamic variables, such as pressure, temperature, or entropy, likewise undergo thermal fluctuations. For example, for a system that has an equilibriu ...
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First Law Of Thermodynamics
The first law of thermodynamics is a formulation of the law of conservation of energy, adapted for thermodynamic processes. It distinguishes in principle two forms of energy transfer, heat and thermodynamic work for a system of a constant amount of matter. The law also defines the internal energy of a system, an extensive property for taking account of the balance of energies in the system. The law of conservation of energy states that the total energy of any isolated system, which cannot exchange energy or matter, is constant. Energy can be transformed from one form to another, but can be neither created nor destroyed. The first law for a thermodynamic process is often formulated asThe sign convention (Q is heat supplied ''to'' the system but W is work done ''by'' the system) is that of Rudolf Clausius (Equation IIa on page 384 of Clausius, R. (1850)), and it is followed below. :\Delta U = Q - W, where \Delta U denotes the change in the internal energy of a closed system (f ...
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Exact Differential
In multivariate calculus, a differential or differential form is said to be exact or perfect (''exact differential''), as contrasted with an inexact differential, if it is equal to the general differential dQ for some differentiable function Q in an orthogonal coordinate system. An exact differential is sometimes also called a ''total differential'', or a ''full differential'', or, in the study of differential geometry, it is termed an exact form. The integral of an exact differential over any integral path is path-independent, and this fact is used to identify state functions in thermodynamics. Overview Definition Even if we work in three dimensions here, the definitions of exact differentials for other dimensions are structurally similar to the three dimensional definition. In three dimensions, a form of the type :A(x,y,z) \,dx + B(x,y,z) \,dy + C(x,y,z) \,dz is called a differential form. This form is called ''exact'' on an open domain D \subset \mathbb^3 in spac ...
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Finite Difference
A finite difference is a mathematical expression of the form . If a finite difference is divided by , one gets a difference quotient. The approximation of derivatives by finite differences plays a central role in finite difference methods for the numerical solution of differential equations, especially boundary value problems. The difference operator, commonly denoted \Delta is the operator that maps a function to the function \Delta /math> defined by :\Delta x)= f(x+1)-f(x). A difference equation is a functional equation that involves the finite difference operator in the same way as a differential equation involves derivatives. There are many similarities between difference equations and differential equations, specially in the solving methods. Certain recurrence relations can be written as difference equations by replacing iteration notation with finite differences. In numerical analysis, finite differences are widely used for approximating derivatives, and the term " ...
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Chemical Potential
In thermodynamics, the chemical potential of a species is the energy that can be absorbed or released due to a change of the particle number of the given species, e.g. in a chemical reaction or phase transition. The chemical potential of a species in a mixture is defined as the rate of change of free energy of a thermodynamic system with respect to the change in the number of atoms or molecules of the species that are added to the system. Thus, it is the partial derivative of the free energy with respect to the amount of the species, all other species' concentrations in the mixture remaining constant. When both temperature and pressure are held constant, and the number of particles is expressed in moles, the chemical potential is the partial molar Gibbs free energy. At chemical equilibrium or in phase equilibrium, the total sum of the product of chemical potentials and stoichiometric coefficients is zero, as the free energy is at a minimum. In a system in diffusion equilibrium, th ...
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