Message on THE TRUSTEES MEETING

Solvent Stokes’ Shifts Revisited: Application and Comparison of Thompson−Schweizer−Chandler−Song−Marcus Theories with Ooshika−Bakshiev−Lippert Theories

“…The value of S D depends on time via the long time mean ε or the static permittivity (dielectric constant) and the optical frequency ε = n 2 , the square of the refractive index at short times. I realize that these time-asymptotes are no real substitute for a more formal solution to the field theory of our pseudoparticle, which may have to be expressed in the manner of Froehlich or Feynman , in the theory of the “polaron”, here for a dipole, which could thus be called a “dipolaron”, i.e., the stored e-m field excitation in the impurity as “dressed” by phononlike modes of the solvent, which accomplish repolarizations of the solvent “lattice”. The k 0 wave vector might be that of a librational mode of the solvent lattice for dipolar liquids, for example.…”

“…It might be significant that one can probably employ a g ( r ,∞) at equilibrium with the dipole moment of the excited state, which is very different from the g ( r ,0) in equilibrium with the dipole moment of the ground state. This alternative formalism thus bridges to some extent the difference between the “classical” models and the Gaussian fluid model I employed herein. To obtain actually the pure time dependence of χ ( t ) from a dipolaron model, I would have presumably to solve a variational problem as per Feynman , or other path integral approaches to field theory. I propose the value of κ to be similar to the Debye screening length κ D −1 = (∑ n i z i 2 / k T ε) −1/2 (where n i is the concentration of ions of species i and z is the ionic charge), except that it should involve the solvent dipole moment instead of dissolved ionic charges.…”

“…To obtain actually the pure time dependence of χ ( t ) from a dipolaron model, I would have presumably to solve a variational problem as per Feynman , or other path integral approaches to field theory. I propose the value of κ to be similar to the Debye screening length κ D −1 = (∑ n i z i 2 / k T ε) −1/2 (where n i is the concentration of ions of species i and z is the ionic charge), except that it should involve the solvent dipole moment instead of dissolved ionic charges.…”