Brownian motion is the random motion of suspended in a medium (a liquid or a gas). The traditional mathematical formulation of Brownian motion is that of the Wiener process, which is often called Brownian motion, even in mathematical sources.
This motion pattern typically consists of Randomness fluctuations in a particle's position inside a fluid sub-domain, followed by a relocation to another sub-domain. Each relocation is followed by more fluctuations within the new closed volume. This pattern describes a fluid at thermal equilibrium, defined by a given temperature. Within such a fluid, there exists no preferential direction of flow (as in transport phenomena). More specifically, the fluid's overall Linear momentum and Angular momentum momenta remain null over time. The Kinetic energy of the molecular Brownian motions, together with those of molecular rotations and vibrations, sum up to the caloric component of a fluid's internal energy (the equipartition theorem).Pathria, RK (1972). Statistical Mechanics. Pergamon Press. pp. 43–48, 73–74. ISBN 0-08-016747-0.
This motion is named after the Scottish botanist Robert Brown, who first described the phenomenon in 1827, while looking through a microscope at pollen of the plant Clarkia pulchella immersed in water. In 1900, the French mathematician Louis Bachelier modeled the stochastic process now called Brownian motion in his doctoral thesis, The Theory of Speculation (Théorie de la spéculation), prepared under the supervision of Henri Poincaré. Then, in 1905, theoretical physicist Albert Einstein published a paper in which he modelled the motion of the pollen particles as being moved by individual water , making one of his first major scientific contributions.
The direction of the force of atomic bombardment is constantly changing, and at different times the particle is hit more on one side than another, leading to the seemingly random nature of the motion. This explanation of Brownian motion served as convincing evidence that and molecules exist and was further verified experimentally by Jean Perrin in 1908. Perrin was awarded the Nobel Prize in Physics in 1926 "for his work on the discontinuous structure of matter".
The many-body interactions that yield the Brownian pattern cannot be solved by a model accounting for every involved molecule. Consequently, only probabilistic models applied to molecular populations can be employed to describe it. Two such models of the statistical mechanics, due to Einstein and Smoluchowski, are presented below. Another, pure probabilistic class of models is the class of the stochastic process models. There exist sequences of both simpler and more complicated stochastic processes which converge (in the limit) to Brownian motion (see random walk and Donsker's theorem).
Although the mingling, tumbling motion of dust particles is caused largely by air currents, the glittering, jiggling motion of small dust particles is caused chiefly by true Brownian dynamics; Lucretius "perfectly describes and explains the Brownian movement by a wrong example".
The discovery of this phenomenon is credited to the botanist Robert Brown in 1827. Brown was studying plant reproduction when he observed pollen grains of the plant Clarkia pulchella in water under a microscope. These grains contain minute particles on the order of 1/4000th of an inch in size. He observed these particles executing a jittery motion. By repeating the experiment with particles of inorganic matter he was able to rule out that the motion was life-related, although its origin was yet to be explained.
The mathematics of much of stochastic analysis including the mathematics of Brownian motion was introduced by Louis Bachelier in 1900 in his PhD thesis "The theory of speculation", in which he presented an analysis of the stock and option markets. However this work was largely unknown until the 1950s.
Albert Einstein (in one of his 1905 papers) provided an explanation of Brownian motion in terms of atoms and molecules at a time when their existence was still debated. Einstein proved the relation between the probability distribution of a Brownian particle and the diffusion equation. These equations describing Brownian motion were subsequently verified by the experimental work of Jean Baptiste Perrin in 1908, leading to his Nobel prize. Norbert Wiener gave the first complete and rigorous mathematical analysis in 1923, leading to the underlying mathematical concept being called a Wiener process.
The instantaneous velocity of the Brownian motion can be defined as , when , where is the momentum relaxation time.
In 2010, the instantaneous velocity of a Brownian particle (a glass microsphere trapped in air with optical tweezers) was measured successfully. The velocity data verified the Maxwell–Boltzmann velocity distribution, and the equipartition theorem for a Brownian particle.
The first part of Einstein's argument was to determine how far a Brownian particle travels in a given time interval. Classical mechanics is unable to determine this distance because of the enormous number of bombardments a Brownian particle will undergo, roughly of the order of 1014 collisions per second.
He regarded the increment of particle positions in time in a one-dimensional ( x) space (with the coordinates chosen so that the origin lies at the initial position of the particle) as a random variable () with some probability density function (i.e., is the probability density for a jump of magnitude , i.e., the probability density of the particle incrementing its position from to in the time interval ). Further, assuming conservation of particle number, he expanded the number density (number of particles per unit volume around ) at time in a Taylor series,
where the second equality is by definition of . The integral in the first term is equal to one by the definition of probability, and the second and other even terms (i.e. first and other odd moments) vanish because of space symmetry. What is left gives rise to the following relation:
Where the coefficient after the Laplacian, the second moment of probability of displacement , is interpreted as mass diffusivity D:
Then the density of Brownian particles at point at time satisfies the diffusion equation:
Assuming that N particles start from the origin at the initial time t = 0, the diffusion equation has the solution
This expression (which is a normal distribution with the mean and variance usually called Brownian motion ) allowed Einstein to calculate the moments directly. The first moment is seen to vanish, meaning that the Brownian particle is equally likely to move to the left as it is to move to the right. The second moment is, however, non-vanishing, being given by
This equation expresses the mean squared displacement in terms of the time elapsed and the diffusivity. From this expression Einstein argued that the displacement of a Brownian particle is not proportional to the elapsed time, but rather to its square root. His argument is based on a conceptual switch from the "ensemble" of Brownian particles to the "single" Brownian particle: we can speak of the relative number of particles at a single instant just as well as of the time it takes a Brownian particle to reach a given point.
The second part of Einstein's theory relates the diffusion constant to physically measurable quantities, such as the mean squared displacement of a particle in a given time interval. This result enables the experimental determination of the Avogadro number and therefore the size of molecules. Einstein analyzed a dynamic equilibrium being established between opposing forces. The beauty of his argument is that the final result does not depend upon which forces are involved in setting up the dynamic equilibrium.
In his original treatment, Einstein considered an osmotic pressure experiment, but the same conclusion can be reached in other ways.
Consider, for instance, particles suspended in a viscous fluid in a gravitational field. Gravity tends to make the particles settle, whereas diffusion acts to homogenize them, driving them into regions of smaller concentration. Under the action of gravity, a particle acquires a downward speed of , where is the mass of the particle, is the acceleration due to gravity, and is the particle's mobility in the fluid. George Stokes had shown that the mobility for a spherical particle with radius is , where is the dynamic viscosity of the fluid. In a state of dynamic equilibrium, and under the hypothesis of isothermal fluid, the particles are distributed according to the barometric distribution
where is the difference in density of particles separated by a height difference, of , is the Boltzmann constant (the ratio of the universal gas constant, , to the Avogadro constant, ), and is the absolute temperature.
Dynamic equilibrium is established because the more that particles are pulled down by gravity, the greater the tendency for the particles to migrate to regions of lower concentration. The flux is given by Fick's law,
where . Introducing the formula for , we find that
In a state of dynamical equilibrium, this speed must also be equal to . Both expressions for are proportional to , reflecting that the derivation is independent of the type of forces considered. Similarly, one can derive an equivalent formula for identical of charge in a uniform electric field of magnitude , where is replaced with the electrostatic force . Equating these two expressions yields the Einstein relation for the diffusivity, independent of or or other such forces:
Here the first equality follows from the first part of Einstein's theory, the third equality follows from the definition of the Boltzmann constant as , and the fourth equality follows from Stokes's formula for the mobility. By measuring the mean squared displacement over a time interval along with the universal gas constant , the temperature , the viscosity , and the particle radius , the Avogadro constant can be determined.
The type of dynamical equilibrium proposed by Einstein was not new. It had been pointed out previously by J. J. Thomson in his series of lectures at Yale University in May 1903 that the dynamic equilibrium between the velocity generated by a concentration gradient given by Fick's law and the velocity due to the variation of the partial pressure caused when ions are set in motion "gives us a method of determining Avogadro's constant which is independent of any hypothesis as to the shape or size of molecules, or of the way in which they act upon each other".
An identical expression to Einstein's formula for the diffusion coefficient was also found by Walther Nernst in 1888 in which he expressed the diffusion coefficient as the ratio of the osmotic pressure to the ratio of the Friction and the velocity to which it gives rise. The former was equated to the law of van 't Hoff while the latter was given by Stokes's law. He writes for the diffusion coefficient , where is the osmotic pressure and is the ratio of the frictional force to the molecular viscosity which he assumes is given by Stokes's formula for the viscosity. Introducing the ideal gas law per unit volume for the osmotic pressure, the formula becomes identical to that of Einstein's. The use of Stokes's law in Nernst's case, as well as in Einstein and Smoluchowski, is not strictly applicable since it does not apply to the case where the radius of the sphere is small in comparison with the mean free path.
Confirming Einstein's formula experimentally proved difficult.
Initial attempts by Theodor Svedberg in 1906 and 1907 were critiqued by Einstein and by Perrin as not measuring a quantity directly comparable to the formula. Victor Henri in 1908 took cinematographic shots through a microscope and found quantitative disagreement with the formula but again the analysis was uncertain. Einstein's predictions were finally confirmed in a series of experiments carried out by Chaudesaigues in 1908 and Perrin in 1909. The confirmation of Einstein's theory constituted empirical progress for the kinetic theory of heat. In essence, Einstein showed that the motion can be predicted directly from the kinetic model of thermal equilibrium. The importance of the theory lay in the fact that it confirmed the kinetic theory's account of the second law of thermodynamics as being an essentially statistical law.See P. Clark 1976, p. 97
Smoluchowski attempts to answer the question of why a Brownian particle should be displaced by bombardments of smaller particles when the probabilities for striking it in the forward and rear directions are equal.
If the probability of gains and losses follows a binomial distribution,
with equal probabilities of 1/2, the mean total gain is
If is large enough so that Stirling's approximation can be used in the form
then the expected total gain will be
showing that it increases as the square root of the total population.
Suppose that a Brownian particle of mass is surrounded by lighter particles of mass which are traveling at a speed . Then, reasons Smoluchowski, in any collision between a surrounding and Brownian particles, the velocity transmitted to the latter will be . This ratio is of the order of . But we also have to take into consideration that in a gas there will be more than 1016 collisions in a second, and even greater in a liquid where we expect that there will be 1020 collision in one second. Some of these collisions will tend to accelerate the Brownian particle; others will tend to decelerate it. If there is a mean excess of one kind of collision or the other to be of the order of 108 to 1010 collisions in one second, then velocity of the Brownian particle may be anywhere between . Thus, even though there are equal probabilities for forward and backward collisions there will be a net tendency to keep the Brownian particle in motion, just as the ballot theorem predicts.
These orders of magnitude are not exact because they do not take into consideration the velocity of the Brownian particle, , which depends on the collisions that tend to accelerate and decelerate it. The larger is, the greater will be the collisions that will retard it so that the velocity of a Brownian particle can never increase without limit. Could such a process occur, it would be tantamount to a perpetual motion of the second type. And since equipartition of energy applies, the kinetic energy of the Brownian particle, will be equal, on the average, to the kinetic energy of the surrounding fluid particle,
In 1906 Smoluchowski published a one-dimensional model to describe a particle undergoing Brownian motion. The model assumes collisions with where is the test particle's mass and the mass of one of the individual particles composing the fluid. It is assumed that the particle collisions are confined to one dimension and that it is equally probable for the test particle to be hit from the left as from the right. It is also assumed that every collision always imparts the same magnitude of . If is the number of collisions from the right and the number of collisions from the left then after collisions the particle's velocity will have changed by . The multiplicity is then simply given by:
and the total number of possible states is given by . Therefore, the probability of the particle being hit from the right times is:
As a result of its simplicity, Smoluchowski's 1D model can only qualitatively describe Brownian motion. For a realistic particle undergoing Brownian motion in a fluid, many of the assumptions don't apply. For example, the assumption that on average occurs an equal number of collisions from the right as from the left falls apart once the particle is in motion. Also, there would be a distribution of different possible s instead of always just one in a realistic situation.
The Wiener process is characterized by four facts:
An alternative characterisation of the Wiener process is the so-called Lévy characterisation that says that the Wiener process is an almost surely continuous martingale with and quadratic variation
A third characterisation is that the Wiener process has a spectral representation as a sine series whose coefficients are independent random variables. This representation can be obtained using the Kosambi–Karhunen–Loève theorem.
The Wiener process can be constructed as the scaling limit of a random walk, or other discrete-time stochastic processes with stationary independent increments. This is known as Donsker's theorem. Like the random walk, the Wiener process is recurrent in one or two dimensions (meaning that it returns almost surely to any fixed neighborhood of the origin infinitely often) whereas it is not recurrent in dimensions three and higher. Unlike the random walk, it is scale invariance.
A d-dimensional Gaussian free field has been described as "a d-dimensional-time analog of Brownian motion."
In the general case, Brownian motion is a Markov process and described by stochastic integral equations.
Let be a continuous stochastic process on a probability space taking values in . Then the following are equivalent:
For sufficiently long realization times, the expected value of the power spectrum of a single trajectory converges to the formally defined power spectral density but its coefficient of variation tends to This implies the distribution of is broad even in the infinite time limit.
Riemannian manifolds have the property that can be described in polar coordinates; that is, displacements are always in a radial direction, at some given angle. Uniform random motion is then described by Gaussians along the radial direction, independent of the angle, the same as in Euclidean space.
The infinitesimal generator (and hence characteristic operator) of Brownian motion on Euclidean is , where denotes the Laplace operator. Brownian motion on an -dimensional Riemannian manifold can be defined as diffusion on with the characteristic operator given by , half the Laplace–Beltrami operator .
One of the topics of study is a characterization of the Poincaré recurrence time for such systems.
Statistical mechanics theories
Einstein's theory
Smoluchowski model
Langevin equation
Astrophysics: star motion within galaxies
Mathematics
denotes the normal distribution with expected value and variance . The condition that it has independent increments means that if then and are independent random variables. In addition, for some filtration is measurable for all
Statistics
Lévy characterisation
Spectral content
Riemannian manifolds
Narrow escape
See also
Further reading
External links
target="_blank" rel="nofollow"> Large-Scale Brownian Motion Demonstration
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