Aqueous solvation dynamics studied by photon echo spectroscopy
Aqueous solvation dynamics studied by photon echo spectroscopy
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DOI：
10.1063/1.478488
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发表时间：
1999-03-22
影响因子：
4.4
通讯作者：
Fleming, GR
中科院分区：
文献类型：
--
作者：
Lang, MJ;Jordanides, XJ;Fleming, GR
三脉冲光子回波峰移测量研究水溶剂化动力学。介电连续介质理论的新视角[X. Song和D.钱德勒，化学物理杂志108，2594（1998）]有助于描述曙红在水中的系统-浴相互作用。该理论的应用提供了溶剂化能，其在谱密度表示ρ（ω）内使用，以计算实验峰位移。只有溶剂化贡献的ρ（ω），其中溶剂化的大幅幅度发生在类似于30 fs的模拟，是非常符合我们的数据。此外，使用该理论溶剂化谱密度和实验确定的分子内谱密度的模拟产生在整个动态范围内的峰移数据的良好的总模拟。我们的实验结果证实了相互作用引起的极化率效应的预测，通过一个类似的180厘米（-1）的谱密度带，影响初始动力学。(C)1999年美国物理学会。[S0021-9606（99）50312-7]。
Three-pulse photon echo peak shift measurements were employed to study aqueous solvation dynamics. A new perspective of dielectric continuum theory [X. Song and D. Chandler, J. Chem. Phys. 108, 2594 (1998)] aided in characterizing the system-bath interactions of eosin in water. Application of this theory provides solvation energies, which were used within the spectral density representation rho(omega), to calculate the experimental peak shift. Simulations with only solvation contributions to rho(omega), where a substantial amplitude of the solvation occurs within similar to 30 fs, are remarkably consistent with our data. Furthermore, simulations using this theoretical solvation spectral density and an experimentally determined intramolecular spectral density yield an excellent total simulation of the peak shift data over the entire dynamic range. Our experimental results substantiate predictions that interaction-induced polarizability effects, contributing via a similar to 180 cm(-1) band in the spectral density, influence the initial dynamics. (C) 1999 American Institute of Physics. [S0021-9606(99)50312-7].