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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 quantities a ...
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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 di ...
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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 ...
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Electron Spin
In atomic physics, the electron magnetic moment, or more specifically the electron magnetic dipole moment, is the magnetic moment of an electron resulting from its intrinsic properties of spin and electric charge. The value of the electron magnetic moment is The electron magnetic moment has been measured to an accuracy of relative to the Bohr magneton. Magnetic moment of an electron The electron is a charged particle with charge −, where is the unit of elementary charge. Its angular momentum comes from two types of rotation: spin and orbital motion. From classical electrodynamics, a rotating distribution of electric charge produces a magnetic dipole, so that it behaves like a tiny bar magnet. One consequence is that an external magnetic field exerts a torque on the electron magnetic moment that depends on the orientation of this dipole with respect to the field. If the electron is visualized as a classical rigid body in which the mass and charge have identical distribution ...
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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 the st ...
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New Delhi
New Delhi (, , ''Naī Dillī'') is the capital of India and a part of the National Capital Territory of Delhi (NCT). New Delhi is the seat of all three branches of the government of India, hosting the Rashtrapati Bhavan, Parliament House, and the Supreme Court of India. New Delhi is a municipality within the NCT, administered by the NDMC, which covers mostly Lutyens' Delhi and a few adjacent areas. The municipal area is part of a larger 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 both the municipality and the New Delhi district forming a relatively small part of the megacity of Delhi. The National Capital Region is a much larger entity comprising the entire NCT along with adjoining districts in neighbouring states, including Ghaziabad, Noida, Gurgaon and Faridabad. The foundation stone of New De ...
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Covariance
In probability theory and statistics, covariance is a measure of the joint variability of two random variables. If the greater values of one variable mainly correspond with the greater values of the other variable, and the same holds for the lesser values (that is, the variables tend to show similar behavior), the covariance is positive. In the opposite case, when the greater values of one variable mainly correspond to the lesser values of the other, (that is, the variables tend to show opposite behavior), the covariance is negative. The sign of the covariance therefore shows the tendency in the linear relationship between the variables. The magnitude of the covariance is not easy to interpret because it is not normalized and hence depends on the magnitudes of the variables. The normalized version of the covariance, the correlation coefficient, however, shows by its magnitude the strength of the linear relation. A distinction must be made between (1) the covariance of two ra ...
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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 deviatio ...
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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 syst ...
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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 space ...
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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 a large ensembles of microstates 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 of a sam ...
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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'' or ''H''. 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 may be expressed in terms of ...
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