Coulomb interaction classical

There are tliree important varieties of long-range forces electrostatic, induction and dispersion. Electrostatic forces are due to classical Coulombic interactions between the static charge distributions of the two molecules. They are strictly pairwise additive, highly anisotropic, and can be either repulsive or attractive. 

Many problems in force field investigations arise from the calculation of Coulomb interactions with fixed charges, thereby neglecting possible mutual polarization. With that obvious drawback in mind, Ulrich Sternberg developed the COSMOS (Computer Simulation of Molecular Structures) force field [30], which extends a classical molecular mechanics force field by serai-empirical charge calculation based on bond polarization theory [31, 32]. This approach has the advantage that the atomic charges depend on the three-dimensional structure of the molecule. Parts of the functional form of COSMOS were taken from the PIMM force field of Lindner et al., which combines self-consistent field theory for r-orbitals ( nr-SCF) with molecular mechanics [33, 34]. 

If classical Coulombic interactions are assumed among point charges for electrostatic interactions between solute and solvent, and the term for the Cl coefficients (C) is omitted, the solvated Eock operator is reduced to Eq. (6). The significance of this definition of the Eock operator from a variational principle is that it enables us to express the analytical first derivative of the free energy with respect to the nuclear coordinate of the solute molecule R ,... 

Chymotrypsin, 170,171, 172, 173 Classical partition functions, 42,44,77 Classical trajectories, 78, 81 Cobalt, as cofactor for carboxypeptidase A, 204-205. See also Enzyme cofactors Condensed-phase reactions, 42-46, 215 Configuration interaction treatment, 14,30 Conformational analysis, 111-117,209 Conjugated gradient methods, 115-116. See also Energy minimization methods Consistent force field approach, 113 Coulomb integrals, 16, 27 Coulomb interactions, in macromolecules, 109, 123-126... 

The electrostatic theory of interaction between ions or molecules was developed many years ago. The individual particles are assumed to be more or less rigid balls. The forces acting on them are determined by Coulomb s classical law of electrostatics. Summaries can be found in many textbooks, see e.g. 25> 45> 46>. 

The classical potential energy term is just a sum of the Coulomb interaction terms (Equation 2.1) that depend on the various inter-particle distances. The potential energy term in the quantum mechanical operator is exactly the same as in classical mechanics. The operator Hop has now been obtained in terms of second derivatives with respect to Cartesian coordinates and inter-particle distances. If one desires to use other coordinates (e.g., spherical polar coordinates, elliptical coordinates, etc.), a transformation presents no difficulties in principle. The solution of a differential equation, known as the Schrodinger equation, gives the energy levels Emoi of the molecular system... 

For 1, de Broglie s wavelength is small enough compared to the classical collision radius b so that a wave packet can be constructed which, approximately, follows the classical Coulomb trajectory [3]. The opposite limit, where the Sommerfeld parameter Zie hv<, denotes the case of weak Coulomb interaction where the Born approximation may be expected to be valid. 

Compared to all other intermolecular interactions, the Coulomb interaction is described by a simple law, i.e.. Equation 15.2. A theory for Coulombic interaction, therefore, uses the concepts and laws that have been developed in classical electrostatics. However, it is worth pointing out that the dielectric constant is a macroscopic property and it is therefore, in principle, not correct to describe the solvent as a dielectric continuum on the molecular level. Nevertheless, experience has shown that it is in fact a useful approximation. 

Present-day diffraction facilities provide easy access to very low-temperature data collection and hence to an accurate determination of electron densities in crystals. Application of standard theorems of classical physics then provides an evaluation of the Coulombic interaction energies in crystal lattices [27]. These calculations are parameter-less and hence are as accurate as the electron density is. Moreover, for highly polar compounds, typically aminoacid zwitterions and the like, a fortunate coincidence cancels out all other attractive and repulsive contributions, and the Coulombic term almost coincides with the total interaction energy. 

Continuum models are the most efficient way to include condensed-phase effects into quantum-mechanical calculations, and this is typically accomplished by using the self-consistent reaction field (SCRF) approach for the electrostatic component. Therefore it is very common to replace the quantal problem by a classical one in which the electronic energy plus the coulombic interactions of the nuclei, taken together, are modeled by a classical force field—this approach usually called molecular mechanics (MM) (Cramer and Truhlar, 1996). 

Term I denotes the classical electron-electron interaction which is related to Darwin s classical expression when expressed in terms of momenta rather than velocities (21). It comprises Coulombic interactions, magnetic, and retardation terms. Term... 

The bare Coulombic interaction (p = 1) and interactions of charges with rotating dipoles (p = 4) do not fall into this class, and it has been argued for a long time [30] that in this case one expects analytical ( classical ) behavior. This implies that the system can be described by a mean-field Hamiltonian, in which the interaction of a particle is ascribed to the mean field of all other particles, thus ignoring local fluctuations [10]. In real ionic fluids the... 

We turn now to theories of ionic criticality that encompass nonclassical phenomena. Mean-field-like criticality of ionic fluids was debated in 1972 [30] and according to a remark by Friedman in this discussion [69], this subject seems to have attracted attention in 1963. Arguments in favor of a mean-field criticality of ionic systems, at least in part, seem to go back to the work of Kac et al. [288], who showed in 1962 that in D = 1 classical van der Waals behavior is obtained for a potential of the form ionic fluids with attractive and repulsive Coulombic interactions have little in common with the simple Kac fluid. 

Kohn-Sham orbitals (18)), Vn is the external, nuclear potential, and p is the electronic momentum operator. Hence, the first integral represents the kinetic and potential energy of a model system with the same density but without electron-electron interaction. The second term is the classical Coulomb interaction of the electron density with itself. Exc> the exchange-correlation (XC) energy, and ENR are functionals of the density. The exact functional form for Exc is unknown it is defined through equation 1 (79), and some suitable approximation has to be chosen in any practical application of... 

That is, these parameters are represented as classical Coulombic interactions between two pairs of overall electrically neutral charge distributions. For e(i,j) = e(= ) the interaction is between two interpenetrating counter-oriented dipolar distributions. For e(i x j) or e(ijxk) the interaction is between two partially overlapping parallel quadrupolar distributions they seem to be roughly the same size s(- ) for i j k. From the forms here e(- = ) is positive. Presumably e(- ) is positive and larger than... 

MO studies of aromatic nitration cast doubt on the existence of jt-complexes and electron-transfer complexes in liquid-phase nitrations.14 The enthalpy of protonation of aromatic substrates provides a very good index of substrate reactivity to nitration. Coulomb interaction between electrophile and substituent can be a special factor influencing regioselectivity. A detailed DFT study of the reaction of toluene with the nitronium ion has been reported.15 Calculated IR spectra for the Wheland intermediates suggest a classical SE2 mechanism. MO calculations of cationic localization energies for the interaction of monosubstituted benzenes with the nitronium ion correlate with observed product yields.16... 

If classical coulombic interactions are assumed among point charges for electrostatic interactions between solute and solvent, and vector coupling coefficients are properly set to the Hartree-Fock case, this operator is reduced to Equation (4.160). 

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