Integral equations potential scattering

In the previous sections the potential scattering problem has been defined in terms of a Schrodinger differential equation with outgoing spherical-wave boundary conditions. The description and computational methods are analogous to those used for one-electron bound-state problems. In this section we see that the whole problem in the coordinate representation can be written in terms of a single integral equation, which in many ways is easier to understand physically than the differential equation. 

The integral equations for relativistic potential scattering are conveniently written in terms of a four-dimensional notation for the four-component spinor vp). 

The first block, INTERACTION, is devoted to the calculation of electronic energies determining the potential energy surface (PES) on which the nuclear morion takes place. The second l)lock, DYNAMICS, is devoted to the integration of the scattering equations to determine the outcome of the molecular process. The third block, OBSER WBLES. is devoted to the reconstruction of the ol)serr al)le properties of the beam from the calculated dynamical quantities. All these blocks reejuiro not only different skills and expertise but also specialized computer software and hardware. 

Fluid microstructure may be characterized in terms of molecular distribution functions. The local number of molecules of type a at a distance between r and r-l-dr from a molecule of type P is Pa T 9afi(r)dr where Pa/j(r) is the spatial pair correlation function. In principle, flr (r) may be determined experimentally by scattering experiments however, results to date are limited to either pure fluids of small molecules or binary mixtures of monatomic species, and no mixture studies have been conducted near a CP. The molecular distribution functions may also be obtained, for molecules interacting by idealized potentials, from molecular simulations and from integral equation theories. 

Recently Elster, Liu and Thaler (ELT) [El 91] proposed a novel method for dealing with the momentum space Coulomb problem, which is, in principle, exact and may be less prone to numerical difficulties than the VP method. Their approach is based on the separation of the optical potential in eq. (3.63) and employs the two-potential formula [Ro 67] to express the full scattering amplitude as a sum of the point Coulomb amplitude and the point Coulomb distorted nuclear amplitude. The latter is obtained by numerically solving an integral equation represented in terms of Coulomb wave function basis states rather than the usual plane wave states. 

Numerical integration of the radial Schrodinger equation is generally necessary if realistic interaction potentials are selected. For this purpose, efficient computer codes exist based, for example, on Cooley s method of integration. Other widely available codes written to compute scattering... 

Potential energy surfaces of weakly bound dimers and trimers are the key quantities needed to compute transition frequencies in the high resolution spectra, (differential and integral) scattering cross sections or rate coefficients describing collisional processes between the molecules, or some thermodynamic properties needed to derive equations of state for condensed phases. However, some other quantities governed by weak intermolecular forces are needed to describe intensities in the spectra or, more generally, infrared and Raman spectra of unbound (collisional complexes) of two molecules, and dielectric and refractive properties of condensed phases. These are the interaction-induced (or collision-induced) dipole moments and polarizabilities. 

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