## Abstract

In cases where dielectric relaxation dominates the time scale of molecular processes which involve the motion of charge (e.g., solvation dynamics, electron transfer reactions, or chemical reactions), the relevant time scale is the longitudinal relaxation time τ_{L}, which is generally faster than the dielectric relaxation time τ_{D}. Numerical calculations of the polarizations P_{D}(t) with dE(t)/dt = 0 and P_{E}(t) with dD(t)/dt = 0 for an electrical RC network equivalent to an arbitrary dielectric function ε*(ω) are performed in order to generalize the relation between τ_{L} and τ_{D} which only for the Debye case reads τ_{L} = τ_{D}ε_{∞}/ε_{s}. The results for non-Debye systems as a function of relaxation time dispersion and relaxation strength are that 〈τ_{L}〉 ≪ 〈τ_{D}〉ε_{∞}/ε_{s} whereas the decay profiles for P_{D}(t) and P_{E}(t) are similar. The normalized field decay P_{E}(t) represents a continuum model prediction for the Stokes shift correlation function C(t) observed in solvation dynamics experiments.

Original language | English (US) |
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Pages (from-to) | 10948-10951 |

Number of pages | 4 |

Journal | Journal of physical chemistry |

Volume | 99 |

Issue number | 27 |

DOIs | |

State | Published - Jan 1 1995 |

Externally published | Yes |

## ASJC Scopus subject areas

- Engineering(all)
- Physical and Theoretical Chemistry