Measurements of the complete solvation response of coumarin 153 in ionic liquids and the accuracy of simple dielectric continuum predictions

被引:83
作者
Maroncelli, Mark [1 ]
Zhang, Xin-Xing [2 ,3 ]
Liang, Min [1 ]
Roy, Durba [1 ]
Ernsting, Nikolaus P. [2 ]
机构
[1] Penn State Univ, Dept Chem, University Pk, PA USA
[2] Humboldt Univ, D-1086 Berlin, Germany
[3] Nankai Univ, Coll Phys Sci, Tianjin 300071, Peoples R China
关键词
POLAR SOLVATION; DYNAMICS; RELAXATION; FLUORESCENCE; FEMTOSECOND; SIMULATION; MOLECULES; ROTATION; DIPOLE; FLUIDS;
D O I
10.1039/c1fd00058f
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The complete solvation response of coumarin 153 (C153) has been determined over the range 10(-13)-10(-8) s in a variety of ionic liquids by combining femtosecond broad-band fluorescence upconversion and picosecond time-correlated single photon counting measurements. These data are used together with recently reported dielectric data in eight ionic liquids to test the accuracy of a simple continuum model for predicting solvation dynamics. In most cases the features of the solvation response functions predicted by the dielectric continuum model are similar to the measured dynamics of C153. The predicted dynamics are, however, systematically faster than those observed, on average by a factor of 3-5. Computer simulations of a model solute/ionic liquid system also exhibit the same relationship between dielectric predictions and observed dynamics. The simulations point to spatial dispersion of the polarization response as an important contributor to the over-prediction of solvation rates in ionic liquids.
引用
收藏
页码:409 / 424
页数:16
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