Energy flow in push-pull chromophores: vibrational dynamics in para-nitroaniline.

Energy flow in push-pull chromophores: vibrational dynamics in para-nitroaniline.
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推拉发色团中的能量流:对硝基苯胺中的振动动力学。

DOI:
10.1002/cphc.200400288
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发表时间:
2005
期刊:
Chemphyschem : a European journal of chemical physics and physical chemistry
影响因子:
--
通讯作者:
Simpson,MCather
Simpson,MCather
中科院分区:
--
文献类型:
--
作者:
Gunaratne,Tissa;Challa,JReddy;Simpson,MCather

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对硝基苯胺(PNA)作为推拉发色团的原型模型起着重要作用。振动自由度在电荷转移和内转换过程中的性质和参与程度是当前具有重要理论和实践意义的问题。采用三种不同激发波长的超快时间分辨反斯托克斯共振拉曼光谱(TRARRS)对二甲亚砜中PNA的动力学影响进行了研究。与s0相关的振动动力学与入射波长无关,这支持了s1动力学相对于系统间交叉速率快的观点。苯基呼吸模式ν19(860 cm−1)和对称no2拉伸模式ν29(1310 cm−1)的振动寿命分别为8.1和5.2 ps。在紫外/可见吸收光谱中没有发现电荷转移带非均匀展宽的证据。
para‐Nitroaniline (PNA) plays an essential role as the prototype model of push–pull chromophores. The nature and degree of participation of vibrational degrees of freedom in the charge‐transfer and internal‐conversion processes are current issues of great theoretical and practical importance. Ultrafast time‐resolved anti‐Stokes resonance Raman spectroscopy (TRARRS) experiments on PNA in dimethyl sulfoxide with three different excitation wavelengths were performed to probe these dynamical influences. The vibrational dynamics associated with S0were independent of incident wavelength, and this supports the picture that the S1dynamics are fast relative to the rate of intersystem crossing. The phenyl breathing modeν19(860 cm−1) and the symmetric NO2stretchν29(1310 cm−1) exhibited vibrational lifetimes in S0of 8.1 and 5.2 ps, respectively. No evidence for inhomogeneous broadening of the charge‐transfer band in the UV/Vis absorption spectrum was found.
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