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Fragmentation of Valence and Core–Shell (Cl 2p) Excited C2Cl4 Molecule
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2017-05-17 00:00:00 , DOI: 10.1021/acs.jpca.7b02632
A. C. F. Santos 1, 2 , M. A. MacDonald 2 , A. B. Rocha 3 , N. Appathurai 2 , M. M. Sant’Anna 1 , W. Holetz 1 , R. Wehlitz 4 , L. Zuin 2
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2017-05-17 00:00:00 , DOI: 10.1021/acs.jpca.7b02632
A. C. F. Santos 1, 2 , M. A. MacDonald 2 , A. B. Rocha 3 , N. Appathurai 2 , M. M. Sant’Anna 1 , W. Holetz 1 , R. Wehlitz 4 , L. Zuin 2
Affiliation
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The dynamics of the photofragmentation pathways of tetrachloroethylene with photon energies from 15 up to 250 eV encompassing the Cl 2p edge is presented. In order to distinguish the fragmentation channels, the ionic fragments were separated according to their mass-to-charge ratio, measured in coincidence with the photoelectrons, and collected as a function of the incident photon energy. Distinct minima or maxima are found in the partial ion yield in the region between 40 and 50 eV. These features are believed to be associated with the Cooper minimum which results from a molecular orbital with a strong atomic 3p subshell character. In the shallow core region, some fragmentation patterns are considered in terms of fast fragmentation of the C2Cl4 molecule, despite the heavy mass of its fragments. In the present case, the fast fragmentation is favored by the very strong antibonding character of the LUMO, understandable in the frame of the core equivalent model for halogen-containing molecules. In addition, ab initio calculations were performed to obtain states at the Cl 2p edge. Singlet and triplet states at the Cl 2p edge of the C2Cl4 molecule, corresponding to the Cl(2p → 9b1u*) and Cl(2p → 8b2u*) transitions, were calculated in order to form a basis set of molecular states from which the spin–orbit splitting can be inferred. Multiconfigurational self-consistent field (MCSCF) calculation followed by multireference configuration interaction (MRCI) was the method chosen to establish a set of singlet and triplet states at the 2p excitation edge in addition to the ground state.
中文翻译：
价核和壳核（Cl 2p）激发的C 2 Cl 4分子的断裂
介绍了四氯乙烯的光致碎裂途径的动态，光子能量从15到250 eV，包括Cl 2p边缘。为了区分碎片通道，根据离子的质荷比将其分离，并与光电子同时测量，并根据入射光子能量进行收集。在40至50 eV之间的部分离子产率中发现了不同的最小值或最大值。这些特征被认为与库珀极小有关，库珀极小是由具有强原子3p子壳特征的分子轨道产生的。在浅层岩心区域，考虑到一些碎裂模式，考虑到C 2 Cl 4的快速碎裂分子，尽管其碎片很重。在当前情况下，LUMO的非常强的抗键合特性有助于快速裂解，这在含卤素分子的核心当量模型的框架中可以理解。另外，进行从头算来获得Cl 2p边缘的状态。C 2 Cl 4分子的Cl 2p边缘的单重态和三重态，对应于Cl（2p→9b 1u *）和Cl（2p→8b 2u*）跃迁是为了形成分子状态的基础集而计算出的，据此可以推断出自旋轨道分裂。选择多配置自洽场（MCSCF），然后进行多参考配置交互（MRCI）是除基态之外在2p激发边缘建立一组单重态和三重态的方法。
更新日期：2017-05-24
中文翻译：
价核和壳核（Cl 2p）激发的C 2 Cl 4分子的断裂
介绍了四氯乙烯的光致碎裂途径的动态，光子能量从15到250 eV，包括Cl 2p边缘。为了区分碎片通道，根据离子的质荷比将其分离，并与光电子同时测量，并根据入射光子能量进行收集。在40至50 eV之间的部分离子产率中发现了不同的最小值或最大值。这些特征被认为与库珀极小有关，库珀极小是由具有强原子3p子壳特征的分子轨道产生的。在浅层岩心区域，考虑到一些碎裂模式，考虑到C 2 Cl 4的快速碎裂分子，尽管其碎片很重。在当前情况下，LUMO的非常强的抗键合特性有助于快速裂解，这在含卤素分子的核心当量模型的框架中可以理解。另外，进行从头算来获得Cl 2p边缘的状态。C 2 Cl 4分子的Cl 2p边缘的单重态和三重态，对应于Cl（2p→9b 1u *）和Cl（2p→8b 2u*）跃迁是为了形成分子状态的基础集而计算出的，据此可以推断出自旋轨道分裂。选择多配置自洽场（MCSCF），然后进行多参考配置交互（MRCI）是除基态之外在2p激发边缘建立一组单重态和三重态的方法。
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