Sticking coefficient is the term used in surface physics to describe the ratio of the number of adsorbate atoms (or molecules) that adsorb, or "stick", to a surface to the total number of atoms that impinge upon that surface during the same period of time. [1] Sometimes the symbol Sc is used to denote this coefficient, and its value is between 1 (all impinging atoms stick) and 0 (no atoms stick). The coefficient is a function of surface temperature, surface coverage (θ) and structural details as well as the kinetic energy of the impinging particles. The original formulation was for molecules adsorbing from the gas phase and the equation was later extended to adsorption from the liquid phase by comparison with molecular dynamics simulations. [2] For use in adsorption from liquids the equation is expressed based on solute density (molecules per volume) rather than the pressure.
When arriving at a site of a surface, an adatom has three options. There is a probability that it will adsorb to the surface (), a probability that it will migrate to another site on the surface (), and a probability that it will desorb from the surface and return to the bulk gas (). For an empty site (θ=0) the sum of these three options is unity.
For a site already occupied by an adatom (θ>0), there is no probability of adsorbing, and so the probabilities sum as:
For the first site visited, the P of migrating overall is the P of migrating if the site is filled plus the P of migrating if the site is empty. The same is true for the P of desorption. The P of adsorption, however, does not exist for an already filled site.
The P of migrating from the second site is the P of migrating from the first site and then migrating from the second site, and so we multiply the two values.
Thus the sticking probability () is the P of sticking of the first site, plus the P of migrating from the first site and then sticking to the second site, plus the P of migrating from the second site and then sticking at the third site etc.
There is an identity we can make use of.
The sticking coefficient when the coverage is zero can be obtained by simply setting . We also remember that
If we just look at the P of migration at the first site, we see that it is certainty minus all other possibilities.
Using this result, and rearranging, we find:
In physics, the cross section is a measure of the probability that a specific process will take place in a collision of two particles. For example, the Rutherford cross-section is a measure of probability that an alpha particle will be deflected by a given angle during an interaction with an atomic nucleus. Cross section is typically denoted σ (sigma) and is expressed in units of area, more specifically in barns. In a way, it can be thought of as the size of the object that the excitation must hit in order for the process to occur, but more exactly, it is a parameter of a stochastic process.
In statistics, maximum likelihood estimation (MLE) is a method of estimating the parameters of an assumed probability distribution, given some observed data. This is achieved by maximizing a likelihood function so that, under the assumed statistical model, the observed data is most probable. The point in the parameter space that maximizes the likelihood function is called the maximum likelihood estimate. The logic of maximum likelihood is both intuitive and flexible, and as such the method has become a dominant means of statistical inference.
In probability theory and statistics, the gamma distribution is a versatile two-parameter family of continuous probability distributions. The exponential distribution, Erlang distribution, and chi-squared distribution are special cases of the gamma distribution. There are two equivalent parameterizations in common use:
Adsorption is the adhesion of atoms, ions or molecules from a gas, liquid or dissolved solid to a surface. This process creates a film of the adsorbate on the surface of the adsorbent. This process differs from absorption, in which a fluid is dissolved by or permeates a liquid or solid. While adsorption does often precede absorption, which involves the transfer of the absorbate into the volume of the absorbent material, alternatively, adsorption is distinctly a surface phenomenon, wherein the adsorbate does not penetrate through the material surface and into the bulk of the adsorbent. The term sorption encompasses both adsorption and absorption, and desorption is the reverse of sorption.
In information geometry, the Fisher information metric is a particular Riemannian metric which can be defined on a smooth statistical manifold, i.e., a smooth manifold whose points are probability measures defined on a common probability space. It can be used to calculate the informational difference between measurements.
In mathematical statistics, the Kullback–Leibler (KL) divergence, denoted , is a type of statistical distance: a measure of how much a model probability distribution Q is different from a true probability distribution P. Mathematically, it is defined as
Brunauer–Emmett–Teller (BET) theory aims to explain the physical adsorption of gas molecules on a solid surface and serves as the basis for an important analysis technique for the measurement of the specific surface area of materials. The observations are very often referred to as physical adsorption or physisorption. In 1938, Stephen Brunauer, Paul Hugh Emmett, and Edward Teller presented their theory in the Journal of the American Chemical Society. BET theory applies to systems of multilayer adsorption that usually utilizes a probing gas (called the adsorbate) that does not react chemically with the adsorptive (the material upon which the gas attaches to) to quantify specific surface area. Nitrogen is the most commonly employed gaseous adsorbate for probing surface(s). For this reason, standard BET analysis is most often conducted at the boiling temperature of N2 (77 K). Other probing adsorbates are also utilized, albeit less often, allowing the measurement of surface area at different temperatures and measurement scales. These include argon, carbon dioxide, and water. Specific surface area is a scale-dependent property, with no single true value of specific surface area definable, and thus quantities of specific surface area determined through BET theory may depend on the adsorbate molecule utilized and its adsorption cross section.
The sticking probability is the probability that molecules are trapped on surfaces and adsorb chemically. From Langmuir's adsorption isotherm, molecules cannot adsorb on surfaces when the adsorption sites are already occupied by other molecules, so the sticking probability can be expressed as follows:
In biochemistry and pharmacology, the Hill equation refers to two closely related equations that reflect the binding of ligands to macromolecules, as a function of the ligand concentration. A ligand is "a substance that forms a complex with a biomolecule to serve a biological purpose", and a macromolecule is a very large molecule, such as a protein, with a complex structure of components. Protein-ligand binding typically changes the structure of the target protein, thereby changing its function in a cell.
Reactions on surfaces are reactions in which at least one of the steps of the reaction mechanism is the adsorption of one or more reactants. The mechanisms for these reactions, and the rate equations are of extreme importance for heterogeneous catalysis. Via scanning tunneling microscopy, it is possible to observe reactions at the solid gas interface in real space, if the time scale of the reaction is in the correct range. Reactions at the solid–gas interface are in some cases related to catalysis.
In probability theory, the Chinese restaurant process is a discrete-time stochastic process, analogous to seating customers at tables in a restaurant. Imagine a restaurant with an infinite number of circular tables, each with infinite capacity. Customer 1 sits at the first table. The next customer either sits at the same table as customer 1, or the next table. This continues, with each customer choosing to either sit at an occupied table with a probability proportional to the number of customers already there, or an unoccupied table. At time n, the n customers have been partitioned among m ≤ n tables. The results of this process are exchangeable, meaning the order in which the customers sit does not affect the probability of the final distribution. This property greatly simplifies a number of problems in population genetics, linguistic analysis, and image recognition.
Proportional hazards models are a class of survival models in statistics. Survival models relate the time that passes, before some event occurs, to one or more covariates that may be associated with that quantity of time. In a proportional hazards model, the unique effect of a unit increase in a covariate is multiplicative with respect to the hazard rate. The hazard rate at time is the probability per short time dt that an event will occur between and given that up to time no event has occurred yet. For example, taking a drug may halve one's hazard rate for a stroke occurring, or, changing the material from which a manufactured component is constructed, may double its hazard rate for failure. Other types of survival models such as accelerated failure time models do not exhibit proportional hazards. The accelerated failure time model describes a situation where the biological or mechanical life history of an event is accelerated.
Photon polarization is the quantum mechanical description of the classical polarized sinusoidal plane electromagnetic wave. An individual photon can be described as having right or left circular polarization, or a superposition of the two. Equivalently, a photon can be described as having horizontal or vertical linear polarization, or a superposition of the two.
Rotational diffusion is the rotational movement which acts upon any object such as particles, molecules, atoms when present in a fluid, by random changes in their orientations. Although the directions and intensities of these changes are statistically random, they do not arise randomly and are instead the result of interactions between particles. One example occurs in colloids, where relatively large insoluble particles are suspended in a greater amount of fluid. The changes in orientation occur from collisions between the particle and the many molecules forming the fluid surrounding the particle, which each transfer kinetic energy to the particle, and as such can be considered random due to the varied speeds and amounts of fluid molecules incident on each individual particle at any given time.
Surface-extended X-ray absorption fine structure (SEXAFS) is the surface-sensitive equivalent of the EXAFS technique. This technique involves the illumination of the sample by high-intensity X-ray beams from a synchrotron and monitoring their photoabsorption by detecting in the intensity of Auger electrons as a function of the incident photon energy. Surface sensitivity is achieved by the interpretation of data depending on the intensity of the Auger electrons instead of looking at the relative absorption of the X-rays as in the parent method, EXAFS.
The Langmuir adsorption model explains adsorption by assuming an adsorbate behaves as an ideal gas at isothermal conditions. According to the model, adsorption and desorption are reversible processes. This model even explains the effect of pressure; i.e., at these conditions the adsorbate's partial pressure is related to its volume V adsorbed onto a solid adsorbent. The adsorbent, as indicated in the figure, is assumed to be an ideal solid surface composed of a series of distinct sites capable of binding the adsorbate. The adsorbate binding is treated as a chemical reaction between the adsorbate gaseous molecule and an empty sorption site S. This reaction yields an adsorbed species with an associated equilibrium constant :
In probability theory and directional statistics, a wrapped probability distribution is a continuous probability distribution that describes data points that lie on a unit n-sphere. In one dimension, a wrapped distribution consists of points on the unit circle. If is a random variate in the interval with probability density function (PDF) , then is a circular variable distributed according to the wrapped distribution and is an angular variable in the interval distributed according to the wrapped distribution .
Adsorption is the adhesion of ions or molecules onto the surface of another phase. Adsorption may occur via physisorption and chemisorption. Ions and molecules can adsorb to many types of surfaces including polymer surfaces. A polymer is a large molecule composed of repeating subunits bound together by covalent bonds. In dilute solution, polymers form globule structures. When a polymer adsorbs to a surface that it interacts favorably with, the globule is essentially squashed, and the polymer has a pancake structure.
In statistics, when selecting a statistical model for given data, the relative likelihood compares the relative plausibilities of different candidate models or of different values of a parameter of a single model.
Dissociative adsorption is a process in which a molecule adsorbs onto a surface and simultaneously dissociates into two or more fragments. This process is the basis of many applications, particularly in heterogeneous catalysis reactions. The dissociation involves cleaving of the molecular bonds in the adsorbate, and formation of new bonds with the substrate.