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Conical Intersection
In quantum chemistry, a conical intersection of two or more potential energy surfaces is the set of molecular geometry points where the potential energy surfaces are degenerate (intersect) and the non-adiabatic couplings between these states are non-vanishing. In the vicinity of conical intersections, the Born–Oppenheimer approximation breaks down and the coupling between electronic and nuclear motion becomes important, allowing non-adiabatic processes to take place. The location and characterization of conical intersections are therefore essential to the understanding of a wide range of important phenomena governed by non-adiabatic events, such as photoisomerization, photosynthesis, vision and the photostability of DNA. The conical intersection involving the ground electronic state potential energy surface of the C6H3F3+ molecular ion is discussed in connection with the Jahn–Teller effect in Section 13.4.2 on pages 380-388 of the textbook by Bunker and Jensen. Conical inters ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Avoided Crossing
In quantum physics and quantum chemistry, an avoided crossing (sometimes called intended crossing, ''non-crossing'' or anticrossing) is the phenomenon where two eigenvalues of an Hermitian matrix representing a quantum observable and depending on ''N'' continuous real parameters cannot become equal in value ("cross") except on a manifold of ''N''-2 dimensions. The phenomenon is also known as the von Neumann–Wigner theorem. In the case of a diatomic molecule (with one parameter, namely the bond length), this means that the eigenvalues cannot cross at all. In the case of a triatomic molecule, this means that the eigenvalues can coincide only at a single point (see conical intersection). This is particularly important in quantum chemistry. In the Born–Oppenheimer approximation, the electronic molecular Hamiltonian is diagonalized on a set of distinct molecular geometries (the obtained eigenvalues are the values of the adiabatic potential energy surfaces). The geometries for which ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
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] |
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] |
Bond Hardening
Bond hardening is a process of creating a new chemical bond by strong laser fields—an effect opposite to bond softening. However, it is not opposite in the sense that the bond becomes stronger, but in the sense that the molecule enters a state that is diametrically opposite to the bond-softened state. Such states require laser pulses of high intensity, in the range of 1013–1015 W/cm2, and they disappear once the pulse is gone. Theory Bond hardening and bond softening share the same theoretical basis, which is described under the latter entry. Briefly, the ground and the first excited energy curves of the H2+ ion are dressed in photons. The laser field perturbs the curves and turns their crossings into anticrossings. Bond softening occurs on the lower branches of the anticrossings and bond hardening happens if the molecule is excited to the upper branches – see Fig. 1. To trap the molecule in the bond-hardened state, the anticrossing gap cannot be too small or too large. ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Bond Softening
Bond softening is an effect of reducing the strength of a chemical bond by strong laser fields. To make this effect significant, the strength of the electric field in the laser light has to be comparable with the electric field the bonding electron "feels" from the nuclei of the molecule. Such fields are typically in the range of 1–10 V/Å, which corresponds to laser intensities 1013–1015 W/cm2. Nowadays, these intensities are routinely achievable from table-top Ti:Sapphire lasers. Theory Theoretical description of bond softening can be traced back to early work on dissociation of diatomic molecules in intense laser fields. While the quantitative description of this process requires quantum mechanics, it can be understood qualitatively using quite simple models. Low-intensity description Consider the simplest diatomic molecule, the H2+ ion. The ground state of this molecule is bonding and the first excited state is antibonding. This means that when we plot the potential ene ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Avoided Crossing
In quantum physics and quantum chemistry, an avoided crossing (sometimes called intended crossing, ''non-crossing'' or anticrossing) is the phenomenon where two eigenvalues of an Hermitian matrix representing a quantum observable and depending on ''N'' continuous real parameters cannot become equal in value ("cross") except on a manifold of ''N''-2 dimensions. The phenomenon is also known as the von Neumann–Wigner theorem. In the case of a diatomic molecule (with one parameter, namely the bond length), this means that the eigenvalues cannot cross at all. In the case of a triatomic molecule, this means that the eigenvalues can coincide only at a single point (see conical intersection). This is particularly important in quantum chemistry. In the Born–Oppenheimer approximation, the electronic molecular Hamiltonian is diagonalized on a set of distinct molecular geometries (the obtained eigenvalues are the values of the adiabatic potential energy surfaces). The geometries for which ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Diabatic
One of the guiding principles in modern chemical dynamics and spectroscopy is that the motion of the nuclei in a molecule is slow compared to that of its electrons. This is justified by the large disparity between the mass of an electron and the typical mass of a nucleus and leads to the Born-Oppenheimer approximation and the idea that the structure and dynamics of a chemical species are largely determined by nuclear motion on potential energy surfaces. The potential energy surfaces are obtained within the adiabatic or Born–Oppenheimer approximation. This corresponds to a representation of the molecular wave function where the variables corresponding to the molecular geometry and the electronic degrees of freedom are separated. The non separable terms are due to the nuclear kinetic energy terms in the molecular Hamiltonian and are said to couple the potential energy surfaces. In the neighbourhood of an avoided crossing or conical intersection, these terms cannot be neglecte ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Christopher Longuet-Higgins
Hugh Christopher Longuet-Higgins (April 11, 1923 – March 27, 2004) was a British scholar and teacher. He was the Professor of Theoretical Chemistry at the University of Cambridge for 13 years until 1967 when he moved to the University of Edinburgh to work in the developing field of cognitive science. He made many significant contributions to our understanding of molecular science. He was also a gifted amateur musician, both as performer and composer, and was keen to advance the scientific understanding of this art. He was the founding editor of the journal ''Molecular Physics''. Education and early life Longuet-Higgins was born on 11 April 1923 at The Vicarage, Lenham, Kent, England, the elder son and second of the three children of Henry Hugh Longuet Longuet-Higgins (1886-1966), vicar of Lenham, and his wife, Albinia Cecil Bazeley. He was educated at The Pilgrims' School, Winchester, and Winchester College. At Winchester College he was one of the "gang of four" consisting o ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Potential Energy Surface
A potential energy surface (PES) describes the energy of a system, especially a collection of atoms, in terms of certain parameters, normally the positions of the atoms. The surface might define the energy as a function of one or more coordinates; if there is only one coordinate, the surface is called a ''potential energy curve'' or energy profile. An example is the Morse/Long-range potential. It is helpful to use the analogy of a landscape: for a system with two degrees of freedom (e.g. two bond lengths), the value of the energy (analogy: the height of the land) is a function of two bond lengths (analogy: the coordinates of the position on the ground). The PES concept finds application in fields such as chemistry and physics, especially in the theoretical sub-branches of these subjects. It can be used to theoretically explore properties of structures composed of atoms, for example, finding the minimum energy shape of a molecule or computing the rates of a chemical reaction. ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Open Shell
In atomic physics and quantum chemistry, the electron configuration is the distribution of electrons of an atom or molecule (or other physical structure) in atomic or molecular orbitals. For example, the electron configuration of the neon atom is , meaning that the 1s, 2s and 2p subshells are occupied by 2, 2 and 6 electrons respectively. Electronic configurations describe each electron as moving independently in an orbital, in an average field created by all other orbitals. Mathematically, configurations are described by Slater determinants or configuration state functions. According to the laws of quantum mechanics, for systems with only one electron, a level of energy is associated with each electron configuration and in certain conditions, electrons are able to move from one configuration to another by the emission or absorption of a quantum of energy, in the form of a photon. Knowledge of the electron configuration of different atoms is useful in understanding the structu ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Orthogonal Complement
In the mathematical fields of linear algebra and functional analysis, the orthogonal complement of a subspace ''W'' of a vector space ''V'' equipped with a bilinear form ''B'' is the set ''W''⊥ of all vectors in ''V'' that are orthogonal to every vector in ''W''. Informally, it is called the perp, short for perpendicular complement. It is a subspace of ''V''. Example Let V = (\R^5, \langle \cdot, \cdot \rangle) be the vector space equipped with the usual dot product \langle \cdot, \cdot \rangle (thus making it an inner product space), and let W = \, with A = \begin 1 & 0\\ 0 & 1\\ 2 & 6\\ 3 & 9\\ 5 & 3\\ \end. then its orthogonal complement W^\perp = \ can also be defined as W^\perp = \, being \tilde = \begin -2 & -3 & -5 \\ -6 & -9 & -3 \\ 1 & 0 & 0 \\ 0 & 1 & 0 \\ 0 & 0 & 1 \end. The fact that every column vector in A is orthogonal to every column vector in \tilde can be checked by direct computation. The fact that the spans of these vectors are orthogonal then follows by b ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
