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多光子反应的线性响应:强飞秒激光脉冲作用下溶液中蒽双自由基的三光子环化反式异构化。

Linear response of multiphoton reaction: three-photon cycloreversion of anthracene biplanemer in solution by intense femtosecond laser pulses.

机构信息

Department of Chemistry, Graduate School of Science, Osaka City University, 3-3-138 Sugimoto, Sumiyoshi, Osaka 558-8585, Japan.

出版信息

J Phys Chem A. 2010 Oct 7;114(39):10475-80. doi: 10.1021/jp1041475.

Abstract

The photocycloreversion of anthracene photodimers and biplanemer in solution was investigated by nonresonant intense femtosecond laser pulses. Cycloreversion of biplanemer showed a pseudolinear response to laser intensity whereas the formation of anthracene from photodimer was proportional to the cubic of laser intensity. The unusual intensity dependence of biplanemer was explained in terms of the sum of three-photon intramolecular cycloreversion and the recovery of reactant by a two-photon intramolecular cyclodimerization. The coexistence of high- and low-order multiphoton processes within the same laser pulse originated in the spatial distribution of the laser intensity. We observed white light emerging from the sample solution; however, the effect of solvated electrons was not observed in the present system. The saturation of both the photoreaction and white light due to a volume effect was observed at high intensity.

摘要

通过非共振强飞秒激光脉冲研究了溶液中蒽光二聚体和双并苯的光环化反转。双并苯的环化反转对激光强度表现出近似线性的响应,而光二聚体生成蒽的速率与激光强度的立方成正比。通过三光子分子内环化和双光子分子内环二聚化的反应物恢复的总和,解释了双并苯异常的强度依赖性。同一激光脉冲内高次和低次多光子过程的共存源于激光强度的空间分布。我们观察到样品溶液中出现白光,但是在当前系统中未观察到溶剂化电子的影响。在高强度下,由于体积效应,光反应和白光都达到饱和。

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