Quasi-Chemical Theory and Implicit Solvent Models for Simulations

A statistical thermodynamic development is given of a new implicit solvent model that avoids the traditional system size limitations of computer simulation of macromolecular solutions with periodic boundary conditions. This implicit solvent model is based upon the quasi-chemical approach, distinct from the common integral equation trunk of the theory of liquid solutions. The physical content of this theory is the hypothesis that a small set of solvent molecules are decisive for these solvation problems. A detailed derivation of the quasi-chemical theory escorts the development of this proposal. The numerical application of the quasi-chemical treatment to Li$^+$ ion hydration in liquid water is used to motivate and exemplify the quasi-chemical theory. Those results underscore the fact that the quasi-chemical approach refines the path for utilization of ion-water cluster results for the statistical thermodynamics of solutions.Comment: 30 pages, contribution to Santa Fe Workshop on Treatment of Electrostatic Interactions in Computer Simulation of Condensed Medi

Cavity-Enhanced Rayleigh Scattering

We demonstrate Purcell-like enhancement of Rayleigh scattering into a single optical mode of a Fabry-Perot resonator for several thermal atomic and molecular gases. The light is detuned by more than an octave, in this case by hundreds of nanometers, from any optical transition, making particle excitation and spontaneous emission negligible. The enhancement of light scattering into the resonator is explained quantitatively as an interference effect of light waves emitted by a classical driven dipole oscillator. Applications of our method include the sensitive, non-destructive in-situ detection of ultracold molecules.Comment: v2: 13 pages, 7 figures, small changes to the text, extended description of the theoretical mode