Crooks Fluctuation Theorem
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Crooks Fluctuation Theorem
The Crooks fluctuation theorem (CFT), sometimes known as the Crooks equation, is an equation in statistical mechanics that relates the work done on a system during a non-equilibrium transformation to the free energy difference between the final and the initial state of the transformation. During the non-equilibrium transformation the system is at constant volume and in contact with a heat reservoir. The CFT is named after the chemist Gavin E. Crooks (then at University of California, Berkeley) who discovered it in 1998. The most general statement of the CFT relates the probability of a space-time trajectory x(t) to the time-reversal of the trajectory \tilde(t). The theorem says if the dynamics of the system satisfies microscopic reversibility, then the forward time trajectory is exponentially more likely than the reverse, given that it produces entropy, : \frac = e^. If one defines a generic reaction coordinate of the system as a function of the Cartesian coordinates of the c ...
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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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Heat Reservoir
A thermal reservoir, also thermal energy reservoir or thermal bath, is a thermodynamic system with a heat capacity so large that the temperature of the reservoir changes relatively little when a much more significant amount of heat is added or extracted. As a conceptual simplification, it effectively functions as an infinite pool of thermal energy at a given, constant temperature. Since it can act as a source and sink of heat, it is often also referred to as a heat reservoir or heat bath. Lakes, oceans and rivers often serve as thermal reservoirs in geophysical processes, such as the weather. In atmospheric science, large air masses in the atmosphere often function as thermal reservoirs. Since the temperature of a thermal reservoir does not change during the heat transfer, the change of entropy in the reservoir is :dS_=\frac. The microcanonical partition sum Z(E) of a heat bath of temperature has the property :Z(E+\Delta E)=Z(E)e^, where k_B is the Boltzmann constant. It th ...
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Gavin E
Gavin is a male given name originating from Scotland. It is a variation on the medieval name Gawain, meaning "God send" or "white hawk" (or falcon). Sir Gawain was a knight of King Arthur's Round Table. ''Sir Gawain and the Green Knight'' is an epic poem connected with King Arthur's Round Table. Gawain beheads the Green Knight who promptly replaces his head and threatens Gawain an identical fate the same time next year. Decapitation figures elsewhere: the Italian name Gavino is the name of an early Christian martyr (San Gavino, Porto Torres, Sardinia) who was beheaded in 300 AD, his head being thrown in the Mediterranean Sea only later reunited and interred with his body. People with the given name People with the surname * Agnes Gavin (1872–1947), Australian actor and screenwriter * Andy Gavin (born 1970), American programmer * Barrie Gavin (born 1935), British film director * Barry Gavin (1944–2017), Australian rules footballer * Bill Gavin (1907–1985), American rad ...
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Microscopic Reversibility
The principle of microscopic reversibility in physics and chemistry is twofold: * First, it states that the microscopic detailed dynamics of particles and fields is time-reversible because the microscopic equations of motion are symmetric with respect to inversion in time (T-symmetry); * Second, it relates to the statistical description of the kinetics of macroscopic or mesoscopic systems as an ensemble of elementary processes: collisions, elementary transitions or reactions. For these processes, the consequence of the microscopic T-symmetry is: ''Corresponding to every individual process there is a reverse process, and in a state of equilibrium the average rate of every process is equal to the average rate of its reverse process.'' History of microscopic reversibility The idea of microscopic reversibility was born together with physical kinetics. In 1872, Ludwig Boltzmann represented kinetics of gases as statistical ensemble of elementary collisions.Boltzmann, L. (1964), Lectures on ...
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Microstate (statistical Mechanics)
In statistical mechanics, a microstate is a specific microscopic configuration of a thermodynamic system that the system may occupy with a certain probability in the course of its thermal fluctuations. In contrast, the macrostate of a system refers to its macroscopic properties, such as its temperature, pressure, volume and density. Treatments on statistical mechanics define a macrostate as follows: a particular set of values of energy, the number of particles, and the volume of an isolated thermodynamic system is said to specify a particular macrostate of it. In this description, microstates appear as different possible ways the system can achieve a particular macrostate. A macrostate is characterized by a probability distribution of possible states across a certain statistical ensemble of all microstates. This distribution describes the probability of finding the system in a certain microstate. In the thermodynamic limit, the microstates visited by a macroscopic system during ...
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T-symmetry
T-symmetry or time reversal symmetry is the theoretical symmetry of physical laws under the transformation of time reversal, : T: t \mapsto -t. Since the second law of thermodynamics states that entropy increases as time flows toward the future, in general, the macroscopic universe does not show symmetry under time reversal. In other words, time is said to be non-symmetric, or asymmetric, except for special equilibrium states when the second law of thermodynamics predicts the time symmetry to hold. However, quantum noninvasive measurements are predicted to violate time symmetry even in equilibrium, contrary to their classical counterparts, although this has not yet been experimentally confirmed. Time ''asymmetries'' generally are caused by one of three categories: # intrinsic to the dynamic physical law (e.g., for the weak force) # due to the initial conditions of the universe (e.g., for the second law of thermodynamics) # due to measurements (e.g., for the noninvasive measur ...
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Joint Probability
Given two random variables that are defined on the same probability space, the joint probability distribution is the corresponding probability distribution on all possible pairs of outputs. The joint distribution can just as well be considered for any given number of random variables. The joint distribution encodes the marginal distributions, i.e. the distributions of each of the individual random variables. It also encodes the conditional probability distributions, which deal with how the outputs of one random variable are distributed when given information on the outputs of the other random variable(s). In the formal mathematical setup of measure theory, the joint distribution is given by the pushforward measure, by the map obtained by pairing together the given random variables, of the sample space's probability measure. In the case of real-valued random variables, the joint distribution, as a particular multivariate distribution, may be expressed by a multivariate cumu ...
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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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Boltzmann Constant
The Boltzmann constant ( or ) is the proportionality factor that relates the average relative kinetic energy of particles in a gas with the thermodynamic temperature of the gas. It occurs in the definitions of the kelvin and the gas constant, and in Planck's law of black-body radiation and Boltzmann's entropy formula, and is used in calculating thermal noise in resistors. The Boltzmann constant has dimensions of energy divided by temperature, the same as entropy. It is named after the Austrian scientist Ludwig Boltzmann. As part of the 2019 redefinition of SI base units, the Boltzmann constant is one of the seven " defining constants" that have been given exact definitions. They are used in various combinations to define the seven SI base units. The Boltzmann constant is defined to be exactly . Roles of the Boltzmann constant Macroscopically, the ideal gas law states that, for an ideal gas, the product of pressure and volume is proportional to the product of amount of ...
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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 ...
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Optical Tweezers
Optical tweezers (originally called single-beam gradient force trap) are scientific instruments that use a highly focused laser beam to hold and move microscopic and sub-microscopic objects like atoms, nanoparticles and droplets, in a manner similar to tweezers. If the object is held in air or vacuum without additional support, it can be called optical levitation. The laser light provides an attractive or repulsive force (typically on the order of pico newtons), depending on the relative refractive index between particle and surrounding medium. Levitation is possible if the force of the light counters the force of gravity. The trapped particles are usually micron-sized, or even smaller. Dielectric and absorbing particles can be trapped, too. Optical tweezers are used in biology and medicine (for example to grab and hold a single bacterium, a cell like a sperm cell or a blood cell, or a molecule like DNA), nanoengineering and nanochemistry (to study and build materials from sing ...
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Jarzynski Equality
The Jarzynski equality (JE) is an equation in statistical mechanics that relates free energy differences between two states and the irreversible work along an ensemble of trajectories joining the same states. It is named after the physicist Christopher Jarzynski (then at the University of Washington and Los Alamos National Laboratory, currently at the University of Maryland) who derived it in 1996. Fundamentally, the Jarzynski equality points to the fact that the fluctuations in the work satisfy certain constraints separately from the average value of the work that occurs in some process. Overview In thermodynamics, the free energy difference \Delta F = F_B - F_A between two states ''A'' and ''B'' is connected to the work ''W'' done on the system through the ''inequality'': : \Delta F \leq W , with equality holding only in the case of a quasistatic process, i.e. when one takes the system from ''A'' to ''B'' infinitely slowly (such that all intermediate states are in thermody ...
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