Femtosecond pump-probe measurements of solvation by hydrogen-bonding interactions

被引：82

作者：

Pines, E

Pines, D

Ma, YZ

Fleming, GR

机构：

[1] Ben Gurion Univ Negev, Dept Chem, IL-84105 Beer Sheva, Israel

[2] Univ Calif Berkeley, Lawrence Berkeley Natl Lab, Dept Chem, Berkeley, CA 94720 USA

来源：

CHEMPHYSCHEM | 2004年 / 5卷 / 09期

关键词：

femtochemistry; hydrogen-bonding interactions; photoacids; pump-probe spectroscopy; solvation dynamics;

D O I：

10.1002/cphc.200301004

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：

An additional ultrafast blue shift in the transient absorption spectra of hydrogen-bonding complexes of a strong photoacid, 8 hydroxypyrene 1,3,6-trisdimethylsulfonamide (HPTA), over the solvation response of the uncomplexed HPTA and also over that of the methoxy derivative of the photoacid (MPTA) in the presence of the hydrogen-bonding base was observed on optical excitation of the photoacid. The additional 55+/-1 fs solvation response was found to be about 35% and 19% of the total C(t) of HPTA in dichloromethane (DCM) when it was hydrogen bonded to dimethylsulfoxide (DMSO) and dioxane, respectively, and about 29% of the total C(t) of HPTA in dichloroethane (DCE) when it was hydrogen-bonded to DMSO. We have assigned this additional dynamic spectral shift to a transient change in the hydrogen bond (O-H...O) that links HPTA to the complexing base, after the electronic excitation of the photoacid.

引用

页码：1315 / 1327

页数：13

共 80 条

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