Tanaka Michinori, Murakami Masanao, Yatsuhashi Tomoyuki, Nakashima Nobuaki
Department of Chemistry, Graduate School of Science, Osaka City University, 3-3-138 Sugimoto, Sumiyoshi, Osaka 558-8585, Japan.
J Chem Phys. 2007 Sep 14;127(10):104314. doi: 10.1063/1.2764078.
Methane derivatives of CH(3)-X (X: H, F, Cl, Br, I, and CN) were ionized and fragmented by an intense femtosecond laser with a 40 fs pulse at 0.8 microm in intensities of 10(13)-10(15) W cm(-2). The curves of the ionization yields of CH(3)-X versus laser intensities have been found to be fitted with an atomic ionization theory (the theory of Perelomov, Popov, and Terent'ev) that has been established to reproduce experimental results well for rare gas atoms. The saturation intensities have been reproduced within a factor of 1.6 of the calculated ones. For molecules with low ionization potentials such as amines, another atomic ionization theory (the theory of Ammosov, Delone, and Krainov) reproduced the saturation intensities. The atomiclike ionization behavior of molecules indicates that the fragmentation occurs after the ionization. The fragmentation mechanisms after the ionization of some molecular ions are discussed.
CH(3)-X(X:H、F、Cl、Br、I和CN)的甲烷衍生物被一台脉冲宽度为40飞秒、波长为0.8微米、强度在10(13)-10(15) W cm(-2)的强飞秒激光电离并碎片化。已发现CH(3)-X的电离产率与激光强度的曲线符合一种原子电离理论(佩列洛莫夫、波波夫和捷连季耶夫理论),该理论已被确立用于很好地再现稀有气体原子的实验结果。饱和强度的再现值与计算值相差在1.6倍以内。对于诸如胺类等电离势较低的分子,另一种原子电离理论(阿莫索夫、德洛内和克拉伊诺夫理论)再现了饱和强度。分子的类原子电离行为表明碎片化发生在电离之后。讨论了一些分子离子电离后的碎片化机制。