TY - JOUR
T1 - Solvation dynamics and the dielectric response in a glass-forming solvent
T2 - from picoseconds to seconds
AU - Richert, R.
AU - Stickel, F.
AU - Fee, R. S.
AU - Maroncelli, M.
N1 - Funding Information:
Financial support by the Deutsche Forschungsge-meinschaft, SonderforschungsbereichS FB 262, and by the Fonds der Chemischen Industrie are gratefully acknowledged.
PY - 1994/10/28
Y1 - 1994/10/28
N2 - We have measured the response times of sol vation dynamics in the range 100 ps to 100 s and the dielectric relaxation covering 10 decades in frequency for the glass-forming solvent 2-methyltetrahydrofuran. In this wide range of solvent viscosities, from the glass transition to beyond the melting point, the mean relaxation times for the two techniques which monitor dipolar orientation are identical within our resolution. For two characteristic decay traces recorded on the time scales of 10 ns and 1 s we compare the observed Stokes-shift dynamics with various theoretical approaches. The decay pattern is reproduced by the dipolar dynamic-mean-spherical-approximation, whereas the absolute time scale of the solvation is mapped by the dielectric polarization itself. For the solvent under study we find almost perfect agreement between experiment and the dipolar dMSA theory if the time scale of the predicted curve is rescaled by a factor of (ε{lunate}∞/ε{lunate}s) 1 2.
AB - We have measured the response times of sol vation dynamics in the range 100 ps to 100 s and the dielectric relaxation covering 10 decades in frequency for the glass-forming solvent 2-methyltetrahydrofuran. In this wide range of solvent viscosities, from the glass transition to beyond the melting point, the mean relaxation times for the two techniques which monitor dipolar orientation are identical within our resolution. For two characteristic decay traces recorded on the time scales of 10 ns and 1 s we compare the observed Stokes-shift dynamics with various theoretical approaches. The decay pattern is reproduced by the dipolar dynamic-mean-spherical-approximation, whereas the absolute time scale of the solvation is mapped by the dielectric polarization itself. For the solvent under study we find almost perfect agreement between experiment and the dipolar dMSA theory if the time scale of the predicted curve is rescaled by a factor of (ε{lunate}∞/ε{lunate}s) 1 2.
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U2 - 10.1016/0009-2614(94)01032-3
DO - 10.1016/0009-2614(94)01032-3
M3 - Article
AN - SCOPUS:0000230637
SN - 0009-2614
VL - 229
SP - 302
EP - 308
JO - Chemical Physics Letters
JF - Chemical Physics Letters
IS - 3
ER -