Brownian Motion

[Rosham Rosebure]

Thismotion pattern typically consists of random 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 and angular momenta remain null over time. The kinetic energies 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).[citation needed]

This motion is named after the 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 (Thorie de la spculation), prepared under the supervision of Henri Poincar. Then, in 1905, theoretical physicist Albert Einstein published a paper where he modeled the motion of the pollen particles as being moved by individual water molecules, making one of his first major scientific contributions.[3]

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 atoms 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".[4]

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.[5] 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).[6][7]

Observe what happens when sunbeams are admitted into a building and shed light on its shadowy places. You will see a multitude of tiny particles mingling in a multitude of ways... their dancing is an actual indication of underlying movements of matter that are hidden from our sight... It originates with the atoms which move of themselves [i.e., spontaneously]. Then those small compound bodies that are least removed from the impetus of the atoms are set in motion by the impact of their invisible blows and in turn cannon against slightly larger bodies. So the movement mounts up from the atoms and gradually emerges to the level of our senses so that those bodies are in motion that we see in sunbeams, moved by blows that remain invisible.

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".[9]

While Jan Ingenhousz described the irregular motion of coal dust particles on the surface of alcohol in 1785, the discovery of this phenomenon is often credited to the botanist Robert Brown in 1827. Brown was studying pollen grains of the plant Clarkia pulchella suspended in water under a microscope when he observed minute particles, ejected by the pollen grains, 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 first person to describe the mathematics behind Brownian motion was Thorvald N. Thiele in a paper on the method of least squares published in 1880. This was followed independently by Louis Bachelier in 1900 in his PhD thesis "The theory of speculation", in which he presented a stochastic analysis of the stock and option markets. The Brownian motion model of the stock market is often cited, but Benoit Mandelbrot rejected its applicability to stock price movements in part because these are discontinuous.[10]

Albert Einstein (in one of his 1905 papers) and Marian Smoluchowski (1906) brought the solution of the problem to the attention of physicists, and presented it as a way to indirectly confirm the existence of atoms and molecules. Their equations describing Brownian motion were subsequently verified by the experimental work of Jean Baptiste Perrin in 1908.

There are two parts to Einstein's theory: the first part consists in the formulation of a diffusion equation for Brownian particles, in which the diffusion coefficient is related to the mean squared displacement of a Brownian particle, while the second part consists in relating the diffusion coefficient to measurable physical quantities.[11] In this way Einstein was able to determine the size of atoms, and how many atoms there are in a mole, or the molecular weight in grams, of a gas.[12] In accordance to Avogadro's law, this volume is the same for all ideal gases, which is 22.414 liters at standard temperature and pressure. The number of atoms contained in this volume is referred to as the Avogadro number, and the determination of this number is tantamount to the knowledge of the mass of an atom, since the latter is obtained by dividing the molar mass of the gas by the Avogadro constant.

The first part of Einstein's argument was to determine how far a Brownian particle travels in a given time interval.[3] 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.[2]

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.

The type of dynamical equilibrium proposed by Einstein was not new. It had been pointed out previously by J. J. Thomson[14] 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".[14]

At first, the predictions of Einstein's formula were seemingly refuted by a series of experiments by Svedberg in 1906 and 1907, which gave displacements of the particles as 4 to 6 times the predicted value, and by Henri in 1908 who found displacements 3 times greater than Einstein's formula predicted.[18] But 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.[19]

These orders of magnitude are not exact because they don't take into consideration the velocity of the Brownian particle, U, which depends on the collisions that tend to accelerate and decelerate it. The larger U 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, M U 2 / 2 \displaystyle MU^2/2 , will be equal, on the average, to the kinetic energy of the surrounding fluid particle, m u 2 / 2 \displaystyle mu^2/2 .

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 ΔVs instead of always just one in a realistic situation.

The diffusion equation yields an approximation of the time evolution of the probability density function associated with the position of the particle going under a Brownian movement under the physical definition. The approximation is valid on short timescales.

The time evolution of the position of the Brownian particle itself is best described using the Langevin equation, an equation that involves a random force field representing the effect of the thermal fluctuations of the solvent on the particle. In Langevin dynamics and Brownian dynamics, the Langevin equation is used to efficiently simulate the dynamics of molecular systems that exhibit a strong Brownian component.

The displacement of a particle undergoing Brownian motion is obtained by solving the diffusion equation under appropriate boundary conditions and finding the rms of the solution. This shows that the displacement varies as the square root of the time (not linearly), which explains why previous experimental results concerning the velocity of Brownian particles gave nonsensical results. A linear time dependence was incorrectly assumed.

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