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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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Exponential Probability Density
Exponential may refer to any of several mathematical topics related to exponentiation, including: *Exponential function, also: **Matrix exponential, the matrix analogue to the above *Exponential decay, decrease at a rate proportional to value *Exponential discounting, a specific form of the discount function, used in the analysis of choice over time *Exponential growth, where the growth rate of a mathematical function is proportional to the function's current value *Exponential map (Riemannian geometry), in Riemannian geometry *Exponential map (Lie theory), in Lie theory *Exponential notation, also known as scientific notation, or standard form *Exponential object, in category theory *Exponential time, in complexity theory *in probability and statistics: **Exponential distribution, a family of continuous probability distributions **Exponentially modified Gaussian distribution, describes the sum of independent Normal distribution, normal and Exponential distribution, exponential rando ...
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System
A system is a group of Interaction, interacting or interrelated elements that act according to a set of rules to form a unified whole. A system, surrounded and influenced by its environment (systems), environment, is described by its boundaries, structure and purpose and expressed in its functioning. Systems are the subjects of study of systems theory and other systems sciences. Systems have several common properties and characteristics, including structure, function(s), behavior and interconnectivity. Etymology The term ''system'' comes from the Latin word ''systēma'', in turn from Greek language, Greek ''systēma'': "whole concept made of several parts or members, system", literary "composition"."σύστημα"
Henry George Liddell, Robert Scott, ''A Greek–English Lexicon'', on Per ...
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Entropy (statistical Thermodynamics)
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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Principle Of Maximum Entropy
The principle of maximum entropy states that the probability distribution which best represents the current state of knowledge about a system is the one with largest entropy, in the context of precisely stated prior data (such as a proposition that expresses testable information). Another way of stating this: Take precisely stated prior data or testable information about a probability distribution function. Consider the set of all trial probability distributions that would encode the prior data. According to this principle, the distribution with maximal information entropy is the best choice. History The principle was first expounded by E. T. Jaynes in two papers in 1957 where he emphasized a natural correspondence between statistical mechanics and information theory. In particular, Jaynes offered a new and very general rationale why the Gibbsian method of statistical mechanics works. He argued that the entropy of statistical mechanics and the information entropy of informati ...
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Isothermal–isobaric Ensemble
The isothermal–isobaric ensemble (constant temperature and constant pressure ensemble) is a statistical mechanical ensemble that maintains constant temperature T \, and constant pressure P \, applied. It is also called the NpT-ensemble, where the number of particles N \, is also kept as a constant. This ensemble plays an important role in chemistry as chemical reactions are usually carried out under constant pressure condition. The NPT ensemble is also useful for measuring the equation of state of model systems whose virial expansion for pressure cannot be evaluated, or systems near first-order phase transitions. Derivation of key properties The partition function for the NpT-ensemble can be derived from statistical mechanics by beginning with a system of N identical atoms described by a Hamiltonian of the form \mathbf^2/2m+U(\mathbf^n) and contained within a box of volume V=L^3. This system is described by the partition function of the canonical ensemble in 3 dimensions: :Z ...
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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 ar ...
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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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Softmax Function
The softmax function, also known as softargmax or normalized exponential function, converts a vector of real numbers into a probability distribution of possible outcomes. It is a generalization of the logistic function to multiple dimensions, and used in multinomial logistic regression. The softmax function is often used as the last activation function of a neural network to normalize the output of a network to a probability distribution over predicted output classes, based on Luce's choice axiom. Definition The softmax function takes as input a vector of real numbers, and normalizes it into a probability distribution consisting of probabilities proportional to the exponentials of the input numbers. That is, prior to applying softmax, some vector components could be negative, or greater than one; and might not sum to 1; but after applying softmax, each component will be in the interval (0, 1), and the components will add up to 1, so that they can be interpreted as probab ...
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Forbidden Transition
In spectroscopy, a forbidden mechanism (forbidden transition or forbidden line) is a spectral line associated with absorption or emission of photons by atomic nuclei, atoms, or molecules which undergo a transition that is not allowed by a particular selection rule but is allowed if the approximation associated with that rule is not made. For example, in a situation where, according to usual approximations (such as the electric dipole approximation for the interaction with light), the process cannot happen, but at a higher level of approximation (e.g. magnetic dipole, or electric quadrupole) the process is allowed but at a low rate. An example is phosphorescent glow-in-the-dark materials, which absorb light and form an excited state whose decay involves a spin flip, and is therefore forbidden by electric dipole transitions. The result is emission of light slowly over minutes or hours. Should an atomic nucleus, atom or molecule be raised to an excited state and should the transitio ...
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Spectral Line
A spectral line is a dark or bright line in an otherwise uniform and continuous spectrum, resulting from emission or absorption of light in a narrow frequency range, compared with the nearby frequencies. Spectral lines are often used to identify atoms and molecules. These "fingerprints" can be compared to the previously collected ones of atoms and molecules, and are thus used to identify the atomic and molecular components of stars and planets, which would otherwise be impossible. Types of line spectra Spectral lines are the result of interaction between a quantum system (usually atoms, but sometimes molecules or atomic nuclei) and a single photon. When a photon has about the right amount of energy (which is connected to its frequency) to allow a change in the energy state of the system (in the case of an atom this is usually an electron changing orbitals), the photon is absorbed. Then the energy will be spontaneously re-emitted, either as one photon at the same frequenc ...
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Spectroscopy
Spectroscopy is the field of study that measures and interprets the electromagnetic spectra that result from the interaction between electromagnetic radiation and matter as a function of the wavelength or frequency of the radiation. Matter waves and acoustic waves can also be considered forms of radiative energy, and recently gravitational waves have been associated with a spectral signature in the context of the Laser Interferometer Gravitational-Wave Observatory (LIGO) In simpler terms, spectroscopy is the precise study of color as generalized from visible light to all bands of the electromagnetic spectrum. Historically, spectroscopy originated as the study of the wavelength dependence of the absorption by gas phase matter of visible light dispersed by a prism. Spectroscopy, primarily in the electromagnetic spectrum, is a fundamental exploratory tool in the fields of astronomy, chemistry, materials science, and physics, allowing the composition, physical structure and e ...
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Degeneracy (quantum Mechanics)
In quantum mechanics, an energy level is degenerate if it corresponds to two or more different measurable states of a quantum system. Conversely, two or more different states of a quantum mechanical system are said to be degenerate if they give the same value of energy upon measurement. The number of different states corresponding to a particular energy level is known as the degree of degeneracy of the level. It is represented mathematically by the Hamiltonian for the system having more than one linearly independent eigenstate with the same energy eigenvalue. When this is the case, energy alone is not enough to characterize what state the system is in, and other quantum numbers are needed to characterize the exact state when distinction is desired. In classical mechanics, this can be understood in terms of different possible trajectories corresponding to the same energy. Degeneracy plays a fundamental role in quantum statistical mechanics. For an -particle system in three dime ...
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