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Surface Hopping
Surface hopping is a mixed quantum-classical technique that incorporates quantum mechanical effects into molecular dynamics simulations. Traditional molecular dynamics assume the Born-Oppenheimer approximation, where the lighter electrons adjust instantaneously to the motion of the nuclei. Though the Born-Oppenheimer approximation is applicable to a wide range of problems, there are several applications, such as photoexcited dynamics, electron transfer, and surface chemistry where this approximation falls apart. Surface hopping partially incorporates the non-adiabatic effects by including excited adiabatic surfaces in the calculations, and allowing for 'hops' between these surfaces, subject to certain criteria. Motivation Molecular dynamics simulations numerically solve the classical equations of motion. These simulations, though, assume that the forces on the electrons are derived solely by the ground adiabatic surface. Solving the time-dependent Schrödinger equation numeri ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Mixed Quantum-classical Dynamics
Mixed quantum-classical (MQC) dynamics is a class of computational theoretical chemistry methods tailored to simulate non- adiabatic (NA) processes in molecular and supramolecular chemistry. Such methods are characterized by: # Propagation of nuclear dynamics through classical trajectories; # Propagation of the electrons (or fast particles) through quantum methods; # A feedback algorithm between the electronic and nuclear subsystems to recover nonadiabatic information. Use of NA-MQC dynamics In the Born-Oppenheimer approximation, the ensemble of electrons of a molecule or supramolecular system can have several discrete states. The potential energy of each of these electronic states depends on the position of the nuclei, forming multidimensional surfaces. Under usual conditions (room temperature, for instance), the molecular system is in the ground electronic state (the electronic state of lowest energy). In this stationary situation, nuclei and electrons are in equilibrium ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Vibrations
Vibration is a mechanical phenomenon whereby oscillations occur about an equilibrium point. The word comes from Latin ''vibrationem'' ("shaking, brandishing"). The oscillations may be periodic, such as the motion of a pendulum—or random, such as the movement of a tire on a gravel road. Vibration can be desirable: for example, the motion of a tuning fork, the reed in a woodwind instrument or harmonica, a mobile phone, or the cone of a loudspeaker. In many cases, however, vibration is undesirable, wasting energy and creating unwanted sound. For example, the vibrational motions of engines, electric motors, or any mechanical device in operation are typically unwanted. Such vibrations could be caused by imbalances in the rotating parts, uneven friction, or the meshing of gear teeth. Careful designs usually minimize unwanted vibrations. The studies of sound and vibration are closely related. Sound, or pressure waves, are generated by vibrating structures (e.g. vocal cords); thes ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Computational Chemistry
Computational chemistry is a branch of chemistry that uses computer simulation to assist in solving chemical problems. It uses methods of theoretical chemistry, incorporated into computer programs, to calculate the structures and properties of molecules, groups of molecules, and solids. It is essential because, apart from relatively recent results concerning the hydrogen molecular ion (dihydrogen cation, see references therein for more details), the quantum many-body problem cannot be solved analytically, much less in closed form. While computational results normally complement the information obtained by chemical experiments, it can in some cases predict hitherto unobserved chemical phenomena. It is widely used in the design of new drugs and materials. Examples of such properties are structure (i.e., the expected positions of the constituent atoms), absolute and relative (interaction) energies, electronic charge density distributions, dipoles and higher multipole moments, ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Electron Excitation
Electron excitation is the transfer of a bound electron to a more energetic, but still bound state. This can be done by photoexcitation (PE), where the electron absorbs a photon and gains all its energy or by collisional excitation (CE), where the electron receives energy from a collision with another, energetic electron. Within a semiconductor crystal lattice, thermal excitation is a process where lattice vibrations provide enough energy to transfer electrons to a higher energy band such as a more energetic sublevel or energy level. When an excited electron falls back to a state of lower energy, it undergoes electron relaxation (deexcitation). This is accompanied by the emission of a photon (radiative relaxation/spontaneous emission) or by a transfer of energy to another particle. The energy released is equal to the difference in energy levels between the electron energy states. In general, the excitation of electrons in atoms strongly varies from excitation in solids, due to t ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Statistical Ensemble (mathematical Physics)
In physics, specifically statistical mechanics, an ensemble (also statistical ensemble) is an idealization consisting of a large number of virtual copies (sometimes infinitely many) of a system, considered all at once, each of which represents a possible state that the real system might be in. In other words, a statistical ensemble is a set of systems of particles used in statistical mechanics to describe a single system. The concept of an ensemble was introduced by J. Willard Gibbs in 1902. A thermodynamic ensemble is a specific variety of statistical ensemble that, among other properties, is in statistical equilibrium (defined below), and is used to derive the properties of thermodynamic systems from the laws of classical or quantum mechanics. Physical considerations The ensemble formalises the notion that an experimenter repeating an experiment again and again under the same macroscopic conditions, but unable to control the microscopic details, may expect to observe a ran ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Phase Space
In dynamical system theory, a phase space is a space in which all possible states of a system are represented, with each possible state corresponding to one unique point in the phase space. For mechanical systems, the phase space usually consists of all possible values of position and momentum variables. It is the outer product of direct space and reciprocal space. The concept of phase space was developed in the late 19th century by Ludwig Boltzmann, Henri Poincaré, and Josiah Willard Gibbs. Introduction In a phase space, every degree of freedom or parameter of the system is represented as an axis of a multidimensional space; a one-dimensional system is called a phase line, while a two-dimensional system is called a phase plane. For every possible state of the system or allowed combination of values of the system's parameters, a point is included in the multidimensional space. The system's evolving state over time traces a path (a phase-space trajectory for the s ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Marcus Theory
In theoretical chemistry, Marcus theory is a theory originally developed by Rudolph A. Marcus, starting in 1956, to explain the rates of electron transfer reactions – the rate at which an electron can move or jump from one chemical species (called the electron donor) to another (called the electron acceptor). It was originally formulated to address outer sphere electron transfer reactions, in which the two chemical species only change in their charge with an electron jumping (e.g. the oxidation of an ion like Fe2+/Fe3+), but do not undergo large structural changes. It was extended to include inner sphere electron transfer contributions, in which a change of distances or geometry in the solvation or coordination shells of the two chemical species is taken into account (the Fe-O distances in Fe(H2O)2+ and Fe(H2O)3+ are different).Hush, N.S. Trans. Faraday Soc. 1961, 57,557 For electron transfer reactions without making or breaking bonds Marcus theory takes the place of Eyring ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Quantum Fluctuation
In quantum physics, a quantum fluctuation (also known as a vacuum state fluctuation or vacuum fluctuation) is the temporary random change in the amount of energy in a point in space, as prescribed by Werner Heisenberg's uncertainty principle. They are minute random fluctuations in the values of the fields which represent elementary particles, such as electric and magnetic fields which represent the electromagnetic force carried by photons, W and Z fields which carry the weak force, and gluon fields which carry the strong force. Vacuum fluctuations appear as virtual particles, which are always created in particle-antiparticle pairs. Since they are created spontaneously without a source of energy, vacuum fluctuations and virtual particles are said to violate the conservation of energy. This is theoretically allowable because the particles annihilate each other within a time limit determined by the uncertainty principle so they are not directly observable. The uncertainty pri ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Conservation Of Energy
In physics and chemistry, the law of conservation of energy states that the total energy of an isolated system remains constant; it is said to be ''conserved'' over time. This law, first proposed and tested by Émilie du Châtelet, means that energy can neither be created nor destroyed; rather, it can only be transformed or transferred from one form to another. For instance, chemical energy is converted to kinetic energy when a stick of dynamite explodes. If one adds up all forms of energy that were released in the explosion, such as the kinetic energy and potential energy of the pieces, as well as heat and sound, one will get the exact decrease of chemical energy in the combustion of the dynamite. Classically, conservation of energy was distinct from conservation of mass. However, special relativity shows that mass is related to energy and vice versa by ''E = mc2'', and science now takes the view that mass-energy as a whole is conserved. Theoretically, this implies that an ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Vibronic Coupling
Vibronic coupling (also called nonadiabatic coupling or derivative coupling) in a molecule involves the interaction between electronic and nuclear vibrational motion. The term "vibronic" originates from the combination of the terms "vibrational" and "electronic", denoting the idea that in a molecule, vibrational and electronic interactions are interrelated and influence each other. The magnitude of vibronic coupling reflects the degree of such interrelation. In theoretical chemistry, the vibronic coupling is neglected within the Born–Oppenheimer approximation. Vibronic couplings are crucial to the understanding of nonadiabatic processes, especially near points of conical intersections. The direct calculation of vibronic couplings is not common due to difficulties associated with its evaluation. Definition Vibronic coupling describes the mixing of different electronic states as a result of small vibrations. : \mathbf_\equiv\langle\,\chi_(\mathbf;\mathbf)\,, \, \hat_\m ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Wavefunction
A wave function in quantum physics is a mathematical description of the quantum state of an isolated quantum system. The wave function is a complex-valued probability amplitude, and the probabilities for the possible results of measurements made on the system can be derived from it. The most common symbols for a wave function are the Greek letters and (lower-case and capital psi, respectively). The wave function is a function of the degrees of freedom corresponding to some maximal set of commuting observables. Once such a representation is chosen, the wave function can be derived from the quantum state. For a given system, the choice of which commuting degrees of freedom to use is not unique, and correspondingly the domain of the wave function is also not unique. For instance, it may be taken to be a function of all the position coordinates of the particles over position space, or the momenta of all the particles over momentum space; the two are related by a Fourie ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Integral
In mathematics, an integral assigns numbers to functions in a way that describes displacement, area, volume, and other concepts that arise by combining infinitesimal data. The process of finding integrals is called integration. Along with differentiation, integration is a fundamental, essential operation of calculus,Integral calculus is a very well established mathematical discipline for which there are many sources. See and , for example. and serves as a tool to solve problems in mathematics and physics involving the area of an arbitrary shape, the length of a curve, and the volume of a solid, among others. The integrals enumerated here are those termed definite integrals, which can be interpreted as the signed area of the region in the plane that is bounded by the graph of a given function between two points in the real line. Conventionally, areas above the horizontal axis of the plane are positive while areas below are negative. Integrals also refer to the concept ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
