Dipole function many-body

As noted in Chapter 2, computation of charge-charge (or dipole-dipole) terms is a particularly efficient means to evaluate electrostatic interactions because it is pairwise additive. However, a more realistic picture of an actual physical system is one that takes into account the polarization of the system. Thus, different regions in a simulation (e.g., different functional groups, or different atoms) will be characterized by different local polarizabilities, and the local charge moments, by adjusting in an iterative fashion to their mutual interactions, introduce many-body effects into a simulation. 

Later studies showed the same phenomena in deuterium and deuterium-rare gas mixtures [335, 338, 305], and also in nitrogen and nitrogen-helium mixtures [336] in nitrogen-argon mixtures the feature is, however, not well developed. The intercollisional dip (as the feature is now commonly called) in the rototranslational spectra was identified many years later see Fig. 3.5 and related discussions. The phenomenon was explained by van Kranendonk [404] as a many-body process, in terms of the correlations of induced dipoles in consecutive collisions. In other words, at low densities, the dipole autocorrelation function has a significant negative tail of a characteristic decay time equal to the mean time between collisions see the theoretical developments in Chapter 5 for details. 

In recent molecular dynamics studies attempts were made to reproduce the shapes of the intercollisional dip from reliable pair dipole models and pair potentials [301], The shape and relative amplitude of the intercollisional dip are known to depend sensitively on the details of the intermolecular interactions, and especially on the dipole function. For a number of very dense ( 1000 amagat) rare gas mixtures spectral profiles were obtained by molecular dynamics simulation that differed significantly from the observed dips. In particular, the computed amplitudes were never of sufficient magnitude. This fact is considered compelling evidence for the presence of irreducible many-body effects, presumably mainly of the induced dipole function. 

It was recently shown that a formal density expansion of space-time correlation functions of quantum mechanical many-body systems is possible in very general terms [297]. The formalism may be applied to collision-induced absorption to obtain the virial expansions of the dipole... 

Raman scattering depends on the time correlation function of the many-body polarizability of the liquid, collective dipole moment. In the case of Raman scattering, an external electric field (from a laser) generates an induced collective dipole in the liquid ... 

The polarizability time correlation function of a liquid will therefore consist of a single-molecule contribution, a DID contribution, and a cross term between the two. The cross term is negative for intermolecular modes, since on the whole the field generated by the molecular dipoles tends to oppose the applied electric field, thus reducing the many-body polarizability of the liquid (23). 

Specific polarization effects, beyond those modelled by a continuum dielectric model and the movement of certain atoms, are neglected in MIF calculations. Many-body effects are also neglected by use of a pair-wise additive energy function. Polarizable force fields are, however, becoming more common in the molecular mechanics force fields used for molecular dynamics simulations, and MIFs could be developed to account for polarizability via changes in charge magnitude or the induction of dipoles upon movement of the probe. 

Furthermore, the works above have initiated several theoretical groups to calculate the electronic part of the magnetic dipole interaction [13, 81-84], obtained from the experimental dipole constant and gj-factor in "Fr (cL Eq. 2). The good agreement generally obtained for the magnetic hyperfine interaction indicate that the electronic wave functions obtained, reliably may be used in the evaluation of the spectroscopic quadrupole moments from the measured quadrupole constants. The value Q 2( "Fr) = -0.19 b, obtained from many-body calculations of the electronic pan of the hyperfine interaction [83], has been used as a reference value in the evaluation spectroscopic quadrupole moments. 

Attempts to represent the three-body interactions for water in terms of an analytic function fitted to ab initio results date back to the work of dementi and Corongiu [191] and Niesar et al. [67]. These authors used about 200 three-body energies computed at the Hartree-Fock level and fitted them to parametrize a simple polarization model in which induced dipoles were generated on each molecule by the electrostatic field of other molecules. Thus, the induction effects were distorted in order to describe the exchange effects. The three-body potentials obtained in this way and their many-body polarization extensions have been used in simulations of liquid water. We know now that the two-body potentials used in that work were insufficiently accurate for a meaningful evaluation of the role of three-body effects. 

The accuracy of the simulation results depends on a suitable choice of the parameters in the potential functions. On account of equation (23.1), an essential restraint of the calculation method is the pair-wise addition of atomic forces. Although effective pair potentials are used, three-body terms and interactions of higher order are neglected. Consequently, the major many-body contributions to the induced dipole interactions in aqueous ionic systems are not modelled accurately. A further simplification is a common application of... 

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