PFI-ZEKE photoelectron spectrum of CH2F2, ionisation potential and ionic fragmentation appearance potentials.
PFI-ZEKE photoelectron spectrum of CH2F2, ionisation potential and ionic fragmentation appearance potentials.
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DOI：
10.1039/b922298g
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发表时间：
2010-03
期刊：
影响因子：
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通讯作者：
Piotr W. Forysinski;P. Zielke;D. Luckhaus;R. Signorell
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文献类型：
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作者：
Piotr W. Forysinski;P. Zielke;D. Luckhaus;R. Signorell
提出了二氟甲烷从绝热电离势（CH(2)F(2)(+) 的 C(2v) 构象异构体的形成）到第一个离子碎裂通道开始的第一个振动分辨脉冲场电离零动能 (PFI-ZEKE) 光电子能谱。报告了阳离子的绝热电离电势 (12.7252 +/- 0.0009 eV) 以及 H 损失产物 (13.065 +/- 0.003 eV) 和 F 损失产物 (14.30 +/- 0.06 eV) 的出现电势的精确值。在 MP2 水平上使用四 zeta 基组进行从头算谐波计算，试图分配新观察到的振动结构，该振动结构以其先前发布的低分辨率形式引起了对其真实起源的众多猜测。三个最低解离通道的绝热电离势和碎裂出现势也在 CCSD(T) 理论的完整基组极限中进行了预测。
The first vibrationally resolved pulsed-field-ionisation zero-kinetic-energy (PFI-ZEKE) photoelectron spectrum of difluoromethane from its adiabatic ionisation potential (formation of the C(2v) conformer of CH(2)F(2)(+)) to the onset of the first ionic fragmentation channel is presented. Precise values for the adiabatic ionisation potential (12.7252 +/- 0.0009 eV) and the appearance potentials of the H loss product (13.065 +/- 0.003 eV) and the F loss product (14.30 +/- 0.06 eV) of the cation are reported. Ab initio harmonic calculations were performed at the MP2 level with quadruple-zeta basis sets in an attempt to assign the newly observed vibrational structure which, in its previously published low resolution form, led to numerous speculations regarding its true origin. The adiabatic ionisation potential and the fragmentation appearance potentials for the three lowest dissociation channels are also predicted in the complete basis set limit of CCSD(T) theory.