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Born–Oppenheimer Approximation
In quantum chemistry and molecular physics, the Born–Oppenheimer (BO) approximation is the best-known mathematical approximation in molecular dynamics. Specifically, it is the assumption that the wave functions of atomic nuclei and electrons in a molecule can be treated separately, based on the fact that the nuclei are much heavier than the electrons. Due to the larger relative mass of a nucleus compared to an electron, the coordinates of the nuclei in a system are approximated as fixed, while the coordinates of the electrons are dynamic. The approach is named after Max Born and J. Robert Oppenheimer who proposed it in 1927, in the early period of quantum mechanics. The approximation is widely used in quantum chemistry to speed up the computation of molecular wavefunctions and other properties for large molecules. There are cases where the assumption of separable motion no longer holds, which make the approximation lose validity (it is said to "break down"), but even then t ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Born Approximation
Generally in scattering theory and in particular in quantum mechanics, the Born approximation consists of taking the incident field in place of the total field as the driving field at each point in the scatterer. The Born approximation is named after Max Born who proposed this approximation in early days of quantum theory development. It is the perturbation method applied to scattering by an extended body. It is accurate if the scattered field is small compared to the incident field on the scatterer. For example, the scattering of radio waves by a light styrofoam column can be approximated by assuming that each part of the plastic is polarized by the same electric field that would be present at that point without the column, and then calculating the scattering as a radiation integral over that polarization distribution. Born approximation to the Lippmann–Schwinger equation The Lippmann–Schwinger equation for the scattering state \vert\rangle with a momentum p and out-going ... [...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 Fourier trans ... [...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_\ma ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Hellmann–Feynman Theorem
In quantum mechanics, the Hellmann–Feynman theorem relates the derivative of the total energy with respect to a parameter, to the expectation value of the derivative of the Hamiltonian with respect to that same parameter. According to the theorem, once the spatial distribution of the electrons has been determined by solving the Schrödinger equation, all the forces in the system can be calculated using classical electrostatics. The theorem has been proven independently by many authors, including Paul Güttinger (1932), Wolfgang Pauli (1933), Hans Hellmann (1937) and Richard Feynman (1939). The theorem states where *\hat_ is a Hamiltonian operator depending upon a continuous parameter \lambda\,, *, \psi_\lambda\rangle, is an eigen-state (eigenfunction) of the Hamiltonian, depending implicitly upon \lambda, *E_\, is the energy (eigenvalue) of the state , \psi_\lambda\rangle, i.e. \hat_, \psi_\lambda\rangle = E_, \psi_\lambda\rangle. Proof This proof of the Hellmann–Feynma ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Eckart Conditions
The Eckart conditions, named after Carl Eckart, simplify the nuclear motion (rovibrational) Hamiltonian that arises in the second step of the Born–Oppenheimer approximation. They make it possible to approximately separate rotation from vibration. Although the rotational and vibrational motions of the nuclei in a molecule cannot be fully separated, the Eckart conditions minimize the coupling close to a reference (usually equilibrium) configuration. The Eckart conditions are explained by Louck and Galbraith and in Section 10.2 of the textbook by Bunker and Jensen, where a numerical example is given. Definition of Eckart conditions The Eckart conditions can only be formulated for a semi-rigid molecule, which is a molecule with a potential energy surface ''V''(R1, R2,..R''N'') that has a well-defined minimum for R''A''0 (A=1,\ldots, N). These equilibrium coordinates of the nuclei—with masses ''M''''A''—are expressed with respect to a fixed orthonormal principal axes frame an ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Adiabatic Theorem
The adiabatic theorem is a concept in quantum mechanics. Its original form, due to Max Born and Vladimir Fock (1928), was stated as follows: :''A physical system remains in its instantaneous eigenstate if a given perturbation is acting on it slowly enough and if there is a gap between the eigenvalue and the rest of the Hamiltonian's spectrum.'' In simpler terms, a quantum mechanical system subjected to gradually changing external conditions adapts its functional form, but when subjected to rapidly varying conditions there is insufficient time for the functional form to adapt, so the spatial probability density remains unchanged. Diabatic vs. adiabatic processes At some initial time t_0 a quantum-mechanical system has an energy given by the Hamiltonian \hat(t_0); the system is in an eigenstate of \hat(t_0) labelled \psi(x,t_0). Changing conditions modify the Hamiltonian in a continuous manner, resulting in a final Hamiltonian \hat(t_1) at some later time t_1. The system will e ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Coulomb Potential
The electric potential (also called the ''electric field potential'', potential drop, the electrostatic potential) is defined as the amount of work energy needed to move a unit of electric charge from a reference point to the specific point in an electric field. More precisely, it is the energy per unit charge for a test charge that is so small that the disturbance of the field under consideration is negligible. Furthermore, the motion across the field is supposed to proceed with negligible acceleration, so as to avoid the test charge acquiring kinetic energy or producing radiation. By definition, the electric potential at the reference point is zero units. Typically, the reference point is earth or a point at infinity, although any point can be used. In classical electrostatics, the electrostatic field is a vector quantity expressed as the gradient of the electrostatic potential, which is a scalar quantity denoted by or occasionally , equal to the electric potential energy ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Molecular Hamiltonian
In atomic, molecular, and optical physics and quantum chemistry, the molecular Hamiltonian is the Hamiltonian operator representing the energy of the electrons and nuclei in a molecule. This operator and the associated Schrödinger equation play a central role in computational chemistry and physics for computing properties of molecules and aggregates of molecules, such as thermal conductivity, specific heat, electrical conductivity, optical, and magnetic properties, and reactivity. The elementary parts of a molecule are the nuclei, characterized by their atomic numbers, ''Z'', and the electrons, which have negative elementary charge, −''e''. Their interaction gives a nuclear charge of ''Z'' + ''q'', where , with ''N'' equal to the number of electrons. Electrons and nuclei are, to a very good approximation, point charges and point masses. The molecular Hamiltonian is a sum of several terms: its major terms are the kinetic energies of the electrons and the Coulomb ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Particle In A Box
In quantum mechanics, the particle in a box model (also known as the infinite potential well or the infinite square well) describes a particle free to move in a small space surrounded by impenetrable barriers. The model is mainly used as a hypothetical example to illustrate the differences between classical and quantum systems. In classical systems, for example, a particle trapped inside a large box can move at any speed within the box and it is no more likely to be found at one position than another. However, when the well becomes very narrow (on the scale of a few nanometers), quantum effects become important. The particle may only occupy certain positive energy levels. Likewise, it can never have zero energy, meaning that the particle can never "sit still". Additionally, it is more likely to be found at certain positions than at others, depending on its energy level. The particle may never be detected at certain positions, known as spatial nodes. The particle in a box mo ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Momentum
In Newtonian mechanics, momentum (more specifically linear momentum or translational momentum) is the product of the mass and velocity of an object. It is a vector quantity, possessing a magnitude and a direction. If is an object's mass and is its velocity (also a vector quantity), then the object's momentum is : \mathbf = m \mathbf. In the International System of Units (SI), the unit of measurement of momentum is the kilogram metre per second (kg⋅m/s), which is equivalent to the newton-second. Newton's second law of motion states that the rate of change of a body's momentum is equal to the net force acting on it. Momentum depends on the frame of reference, but in any inertial frame it is a ''conserved'' quantity, meaning that if a closed system is not affected by external forces, its total linear momentum does not change. Momentum is also conserved in special relativity (with a modified formula) and, in a modified form, in electrodynamics, quantum mechanics, quan ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Kinetic Energy
In physics, the kinetic energy of an object is the energy that it possesses due to its motion. It is defined as the work needed to accelerate a body of a given mass from rest to its stated velocity. Having gained this energy during its acceleration, the body maintains this kinetic energy unless its speed changes. The same amount of work is done by the body when decelerating from its current speed to a state of rest. Formally, a kinetic energy is any term in a system's Lagrangian which includes a derivative with respect to time. In classical mechanics, the kinetic energy of a non-rotating object of mass ''m'' traveling at a speed ''v'' is \fracmv^2. In relativistic mechanics, this is a good approximation only when ''v'' is much less than the speed of light. The standard unit of kinetic energy is the joule, while the English unit of kinetic energy is the foot-pound. History and etymology The adjective ''kinetic'' has its roots in the Greek word κίνησις ''kinesis'', m ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
