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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 quantitie ...
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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. Sometimes called statistical physics or statistical thermodynamics, its applications include many problems in a wide variety of fields such as biology, neuroscience, computer science Computer science is the study of computation, information, and automation. Computer science spans Theoretical computer science, theoretical disciplines (such as algorithms, theory of computation, and information theory) to Applied science, ..., information theory and sociology. Its main purpose is to clarify the properties of matter in aggregate, in terms of physical laws governing atomic motion. 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 microscop ...
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Partition Function (statistical Mechanics)
In physics, a partition function describes the statistics, statistical properties of a system in thermodynamic equilibrium. Partition functions are function (mathematics), functions of the thermodynamic state function, state variables, such as the temperature and volume. Most of the aggregate thermodynamics, thermodynamic variables of the system, such as the energy, total energy, Thermodynamic free 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 Thermodynamic free energy, 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 (systems), environment at fixed temperature, volume, an ...
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Electron Spin
Spin is an intrinsic form of angular momentum carried by elementary particles, and thus by composite particles such as hadrons, atomic nuclei, and atoms. Spin is quantized, and accurate models for the interaction with spin require relativistic quantum mechanics or quantum field theory. The existence of electron spin angular momentum is inferred from experiments, such as the Stern–Gerlach experiment, in which silver atoms were observed to possess two possible discrete angular momenta despite having no orbital angular momentum. The relativistic spin–statistics theorem connects electron spin quantization to the Pauli exclusion principle: observations of exclusion imply half-integer spin, and observations of half-integer spin imply exclusion. Spin is described mathematically as a vector for some particles such as photons, and as a spinor or bispinor for other particles such as electrons. Spinors and bispinors behave similarly to vectors: they have definite magnitudes and ch ...
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Stationary State
A stationary state is a quantum state with all observables independent of time. It is an eigenvector of the energy operator (instead of a quantum superposition of different energies). It is also called energy eigenvector, energy eigenstate, energy eigenfunction, or energy eigenket. It is very similar to the concept of atomic orbital and molecular orbital in chemistry, with some slight differences explained below. Introduction A stationary state is called ''stationary'' because the system remains in the same state as time elapses, in every observable way. For a single-particle Hamiltonian, this means that the particle has a constant probability distribution for its position, its velocity, its spin, etc. (This is true assuming the particle's environment is also static, i.e. the Hamiltonian is unchanging in time.) The wavefunction itself is not stationary: It continually changes its overall complex phase factor, so as to form a standing wave. The oscillation frequency of ...
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New Delhi
New Delhi (; ) is the Capital city, capital of India and a part of the Delhi, National Capital Territory of Delhi (NCT). New Delhi is the seat of all three branches of the Government of India, hosting the Rashtrapati Bhavan, New Parliament House, New Delhi, Sansad Bhavan, and the Supreme Court of India, Supreme Court. New Delhi is a Municipal governance in India, municipality within the NCT, administered by the New Delhi Municipal Council (NDMC), which covers mostly Lutyens' Delhi and a few adjacent areas. The municipal area is part of a larger List of districts in India, administrative district, the New Delhi district. Although colloquially ''Delhi'' and ''New Delhi'' are used interchangeably to refer to the National Capital Territory of Delhi, both are distinct entities, with the municipality and the New Delhi district forming a relatively small part within the megacity of Delhi. The National Capital Region (India), National Capital Region is an even larger entity, compris ...
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Covariance
In probability theory and statistics, covariance is a measure of the joint variability of two random variables. The sign of the covariance, therefore, shows the tendency in the linear relationship between the variables. If greater values of one variable mainly correspond with greater values of the other variable, and the same holds for lesser values (that is, the variables tend to show similar behavior), the covariance is positive. In the opposite case, when greater values of one variable mainly correspond to lesser values of the other (that is, the variables tend to show opposite behavior), the covariance is negative. The magnitude of the covariance is the geometric mean of the variances that are in common for the two random variables. The Pearson product-moment correlation coefficient, correlation coefficient normalizes the covariance by dividing by the geometric mean of the total variances for the two random variables. A distinction must be made between (1) the covariance of ...
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Variance
In probability theory and statistics, variance is the expected value of the squared deviation from the mean of a random variable. The standard deviation (SD) is obtained as the square root of the variance. 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. It is 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 example, the variance of a sum of uncorrelated random variables is equal to the sum of their variances. A disadvantage of the variance for practical applications is that, unlike the standard deviation, its units differ from the random variable, which is why the standard devi ...
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Thermal Fluctuations
In statistical mechanics, thermal fluctuations are random deviations of an atomic 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 equ ...
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First Law Of Thermodynamics
The first law of thermodynamics is a formulation of the law of conservation of energy in the context of thermodynamic processes. For a thermodynamic process affecting a thermodynamic system without transfer of matter, the law distinguishes two principal forms of energy transfer, heat and thermodynamic work. The law also defines the internal energy of a system, an extensive property for taking account of the balance of heat transfer, thermodynamic work, and matter transfer, into and out of the system. Energy cannot be created or destroyed, but it can be transformed from one form to another. In an externally isolated system, with internal changes, the sum of all forms of energy is constant. An equivalent statement is that perpetual motion machines of the first kind are impossible; work done by a system on its surroundings requires that the system's internal energy be consumed, so that the amount of internal energy lost by that work must be resupplied as heat by an external e ...
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Exact Differential
In multivariate calculus, a differential (infinitesimal), 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 coordinates, orthogonal coordinate system (hence Q is a multivariable function Dependent and independent variables#In pure mathematics, whose variables are independent, as they are always expected to be when treated in multivariable calculus). 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 Conservative vector field#Path independence, 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 exa ...
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Gibbs Entropy
The concept entropy was first developed by German physicist Rudolf Clausius in the mid-nineteenth century as a thermodynamic property that predicts that certain spontaneous processes are irreversible or impossible. In statistical mechanics, entropy is formulated as a statistical property using probability theory. The statistical entropy perspective was introduced in 1870 by Austrian physicist Ludwig Boltzmann, who established a new field of physics that provided the descriptive linkage between the macroscopic observation of nature and the microscopic view based on the rigorous treatment of large ensembles of microscopic states that constitute thermodynamic systems. Boltzmann's principle Ludwig Boltzmann defined entropy as a measure of the number of possible microscopic states (''microstates'') of a system in thermodynamic equilibrium, consistent with its macroscopic thermodynamic properties, which constitute the ''macrostate'' of the system. A useful illustration is the example ...
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Fundamental Thermodynamic Relation
In thermodynamics, the fundamental thermodynamic relation are four fundamental equations which demonstrate how four important thermodynamic quantities depend on variables that can be controlled and measured experimentally. Thus, they are essentially equations of state, and using the fundamental equations, experimental data can be used to determine sought-after quantities like ''G'' (Gibbs free energy) or ''H'' (enthalpy). The relation is generally expressed as a microscopic change in internal energy in terms of microscopic changes in entropy, and volume for a closed system in thermal equilibrium in the following way. \mathrmU= T\,\mathrmS - P\,\mathrmV\, Here, ''U'' is internal energy, ''T'' is absolute temperature, ''S'' is entropy, ''P'' is pressure, and ''V'' is volume. This is only one expression of the fundamental thermodynamic relation. It may be expressed in other ways, using different variables (e.g. using thermodynamic potentials). For example, the fundamental relation ...
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