Solvation dynamics for an ion pair in a polar solvent: Time-dependent fluorescence and photochemical charge transfer

• DOI: 10.1063/1.460431
• Publication Date: 2002-07-26T12:20:12Z
• Authors: Emily A. Carter; James T. Hynes

The results of a molecular dynamics (MD) computer simulation are presented for the solvation an ion pair instanteously produced from neutral pair, in model polar aprotic solvent. These time-dependent fluorescence analyzed theoretically to examine validity several linear response theory approaches, as well various theoretical descriptions (e.g., Langevin equation) solvent per se. It is found that these dominated short times by simple inertial Gaussian behavior, feature which absent many current treatments, and related approximate theory. Nonlinear aspects, such overall spectral narrowing, but transient initial broadening, also discussed. A photochemical charge transfer process briefly considered elucidate aspects connection between chemical kinetic population evolution.