### 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) |
---|---|

Pages (from-to) | 10948-10951 |

Number of pages | 4 |

Journal | Journal of Physical Chemistry |

Volume | 99 |

Issue number | 27 |

State | Published - 1995 |

Externally published | Yes |

### Fingerprint

### ASJC Scopus subject areas

- Physical and Theoretical Chemistry

### Cite this

*Journal of Physical Chemistry*,

*99*(27), 10948-10951.

**Polarization response of a dielectric continuum to a motion of charge.** / Richert, Ranko; Wagner, Hermann.

Research output: Contribution to journal › Article

*Journal of Physical Chemistry*, vol. 99, no. 27, pp. 10948-10951.

}

TY - JOUR

T1 - Polarization response of a dielectric continuum to a motion of charge

AU - Richert, Ranko

AU - Wagner, Hermann

PY - 1995

Y1 - 1995

N2 - 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 τL, which is generally faster than the dielectric relaxation time τD. Numerical calculations of the polarizations PD(t) with dE(t)/dt = 0 and PE(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 τL and τD which only for the Debye case reads τL = τDε∞/εs. The results for non-Debye systems as a function of relaxation time dispersion and relaxation strength are that 〈τL〉 ≪ 〈τD〉ε∞/εs whereas the decay profiles for PD(t) and PE(t) are similar. The normalized field decay PE(t) represents a continuum model prediction for the Stokes shift correlation function C(t) observed in solvation dynamics experiments.

AB - 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 τL, which is generally faster than the dielectric relaxation time τD. Numerical calculations of the polarizations PD(t) with dE(t)/dt = 0 and PE(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 τL and τD which only for the Debye case reads τL = τDε∞/εs. The results for non-Debye systems as a function of relaxation time dispersion and relaxation strength are that 〈τL〉 ≪ 〈τD〉ε∞/εs whereas the decay profiles for PD(t) and PE(t) are similar. The normalized field decay PE(t) represents a continuum model prediction for the Stokes shift correlation function C(t) observed in solvation dynamics experiments.

UR - http://www.scopus.com/inward/record.url?scp=0000711870&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0000711870&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0000711870

VL - 99

SP - 10948

EP - 10951

JO - Journal of Physical Chemistry

JF - Journal of Physical Chemistry

SN - 0022-3654

IS - 27

ER -