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强激光脉冲的持续时间能够决定多个化学键的断裂。

Duration of an intense laser pulse can determine the breakage of multiple chemical bonds.

作者信息

Xie Xinhua, Lötstedt Erik, Roither Stefan, Schöffler Markus, Kartashov Daniil, Midorikawa Katsumi, Baltuška Andrius, Yamanouchi Kaoru, Kitzler Markus

机构信息

Photonics Institute, Vienna University of Technology, Gusshausstrasse 27, A-1040 Vienna, Austria, EU.

1] Laser Technology Laboratory, RIKEN, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan [2] RIKEN Center for Advanced Photonics, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan [3] Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.

出版信息

Sci Rep. 2015 Aug 14;5:12877. doi: 10.1038/srep12877.

Abstract

Control over the breakage of a certain chemical bond in a molecule by an ultrashort laser pulse has been considered for decades. With the availability of intense non-resonant laser fields it became possible to pre-determine femtosecond to picosecond molecular bond breakage dynamics by controlled distortions of the electronic molecular system on sub-femtosecond time scales using field-sensitive processes such as strong-field ionization or excitation. So far, all successful demonstrations in this area considered only fragmentation reactions, where only one bond is broken and the molecule is split into merely two moieties. Here, using ethylene (C2H4) as an example, we experimentally investigate whether complex fragmentation reactions that involve the breakage of more than one chemical bond can be influenced by parameters of an ultrashort intense laser pulse. We show that the dynamics of removing three electrons by strong-field ionization determines the ratio of fragmentation of the molecular trication into two respectively three moieties. We observe a relative increase of two-body fragmentations with the laser pulse duration by almost an order of magnitude. Supported by quantum chemical simulations we explain our experimental results by the interplay between the dynamics of electron removal and nuclear motion.

摘要

几十年来,人们一直在考虑用超短激光脉冲控制分子中特定化学键的断裂。随着高强度非共振激光场的出现,通过使用诸如强场电离或激发等场敏感过程,在亚飞秒时间尺度上对电子分子系统进行可控畸变,从而预先确定飞秒到皮秒的分子键断裂动力学成为可能。到目前为止,该领域所有成功的演示都只考虑了碎片化反应,即只有一个键断裂,分子仅分裂成两个部分。在此,我们以乙烯(C₂H₄)为例,通过实验研究涉及多个化学键断裂的复杂碎片化反应是否会受到超短强激光脉冲参数的影响。我们表明,强场电离去除三个电子的动力学决定了分子三价阳离子分裂成两个或三个部分的碎片化比例。我们观察到随着激光脉冲持续时间的增加,双体碎片化的比例相对增加了近一个数量级。在量子化学模拟的支持下,我们通过电子去除动力学和核运动之间的相互作用来解释我们的实验结果。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9ff6/4536518/ce1deaa0c539/srep12877-f1.jpg

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