Ionisation of PF3: absolute partial electron ionisation cross sections and the formation and reactivity of dication states.
Ionisation of PF3: absolute partial electron ionisation cross sections and the formation and reactivity of dication states.
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PF3 的电离：绝对部分电子电离截面以及双阳离子态的形成和反应性。
DOI：
10.1039/d1cp01328a
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发表时间：
2021
期刊：
影响因子：
--
通讯作者：
Ellis-Gibbings LK
中科院分区：
文献类型：
--
作者：
Ellis-Gibbings LK
在电子能量范围50-200 eV内，报道了从三氟化磷（PF 3）形成阳离子的绝对部分电子电离截面和特定于电子的部分电子电离截面。绝对值通过使用2D离子-离子符合飞行时间质谱法测量相对于PF 3+形成的横截面和随后使用总电离横截面的二进制Reichter-Bethe计算进行缩放来确定。这个新的数据集显着增加了部分电离截面的电子电离的PF 3在文献中发现，解决以前的差异的分支比的产品离子，并提供了第一个值的特定的横截面。与文献中计算的截面进行比较是令人鼓舞的，尽管个别离子存在差异。符合实验表明，在200 eV电子能量下，双重和三重电离产生约20%的阳离子电离产物。一个解离的双阳离子态，解离成PF 2 + + F+，被清楚地确定为PF 32+的最低三重态，并且在质谱中检测到五种不同的双阳离子（PF 32+，PF 22+，PF 2+，P2+和F 2+）。由实验揭示的阳离子能量支持的计算调查的阳离子的电子结构。报告的横截面将允许更准确的建模PF 3在高能环境中的电离作用。首次调查的双分子反应性的亚稳态的PF 32+也报道。在与Ar，O2和CO的碰撞解离单电子转移占主导地位的产物离子产率，而碰撞诱导的解离的二价阳离子是重要的碰撞后与Ne。考虑这些过程的能量学表明，反应物双阳离子束包含基态单重态和第一激发三重态的离子。关于三重态寿命的推论得到了符合光谱中亚稳信号的支持。与Ar的PF 32+碰撞后，检测到与ArF+形成对应的弱信号，实验和计算结果表明，这种新的化学键是通过碰撞复合物形成的。
Absolute partial electron ionisation cross sections, and precursor-specific partial electron ionisation cross sections, for the formation of cations from phosphorus trifluoride (PF3) are reported over the electron energy range 50–200 eV. The absolute values are determined by the measurement of cross sections relative to the formation of PF3+ using 2D ion–ion coincidence time-of-flight mass spectrometry and subsequent scaling using binary encounter-Bethe calculations of the total ionisation cross section. This new dataset significantly augments the partial ionisation cross sections for electron ionization of PF3 found in literature, addressing previous discrepancies in the branching ratios of product ions, and provides the first values for the precursor-specific cross sections. Comparisons to calculated cross sections from the literature are encouraging, although there are discrepancies for individual ions. The coincidence experiments indicate that double and triple ionisation generate approximately 20% of the cationic ionisation products at 200 eV electron energy. One dissociative dication state, dissociating to PF2+ + F+, is clearly identified as the lowest triplet state of PF32+ and five different dications (PF32+, PF22+, PF2+, P2+ and F2+) are detected in the mass spectra. The dication energetics revealed by the experiments are supported by a computational investigation of the dication's electronic structure. The cross sections reported will allow more accurate modelling of the role of the ionization of PF3 in energetic environments. A first investigation of the bimolecular reactivity of metastable states of PF32+ is also reported. In collisions with Ar, O2 and CO dissociative single electron transfer dominates the product ion yield, whereas collision-induced dissociation of the dication is important following collisions with Ne. Consideration of the energetics of these processes indicates that the reactant dication beam contains ions in both the ground singlet state and the first excited triplet state. The deduction regarding the longevity of the triplet state is supported by metastable signals in the coincidence spectra. Weak signals corresponding to the formation of ArF+ are detected following PF32+ collisions with Ar, and experimental and computational considerations indicate this new chemical bond is formed via a collision complex.
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DOI：
10.1039/d0cp01194k
发表时间：
2020-04
期刊：
Physical chemistry chemical physics : PCCP
影响因子：
--
作者：
Sam Armenta Butt;S. Price
通讯作者：
Sam Armenta Butt;S. Price
CF32 与氩气碰撞中的电子转移和中性损失反应
影响因子：
1.8
作者：
Nurun Tafadar;N. Kaltsoyannis;S. Price
通讯作者：
S. Price
Elab=49 eV 时 CO++ 与稀有气体的电荷转移和碰撞诱导解离反应
影响因子：
4.4
作者：
S. Rogers;S. Price;S. Leone
通讯作者：
S. Leone
影响因子：
3.3
作者：
Harper, S;Calandra, P;Price, SD
通讯作者：
Price, SD
PF3+ X̃2A1 态的几何结构：实验与理论
影响因子：
2.8
作者：
R. Tuckett;P. Knowles
通讯作者：
P. Knowles