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Lu, Kueih‐Tzu; Chen, J. M.; Lee, J. M.; Chen, S. A.; Liang, Yuan; Chen, S. W.

doi:10.1103/physreva.82.033421

Cited by 9 publications

(21 citation statements)

References 52 publications

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“…The assignment of the first two absorption bands, designated A and B, is done with the help of ab initio calculations in Figure . Band A is related to the transition Cl (2p 3/2 → 10a 1 * - 200.7 eV), in agreement with previous report, while band B, to the Cl (2p 1/2 → 10a 1 * - 202.8 eV). The first transition to 4b 1 * is around 204 eV (2p 3/2 → 4b 1 *).…”

Section: Results and Discussionsupporting

confidence: 92%

“…The first transition to 4b 1 * is around 204 eV (2p 3/2 → 4b 1 *). The two ionization limits due to the spin–orbit splitting of the 2p hole, Cl 2p 3/2,1/2 → ∞ (IP) are designated by the dotted lines at 206.4 and 208.0 eV, respectively.…”

Section: Results and Discussionmentioning

confidence: 99%

“…From Figure 4, one can see that the KER of the CH 2 + ion presents a minimum at the Cl (2P 3/2 → 10a 1 *) resonance. However, it was previously observed 10 that the CH 2 + ion yield (ion production) presents a maximum at the Cl (2P 3/2 → 10a 1 *) resonance, which was interpreted by Lu et al 20 as due to a fast dissociation through a highly repulsive potential curve. Thus, due to the fast dissociation process, the photoelectron takes most of the KER, due to its lower mass.…”

Section: Resultsmentioning

confidence: 99%

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Kinetic Energy Release of the Singly and Doubly Charged Methylene Chloride Molecule: The Role of Fast Dissociation

Alcantara

Rocha

Gomes³

et al. 2016

J. Phys. Chem. A

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The center of mass kinetic energy release distribution (KERD) spectra of selected ionic fragments, formed through dissociative single and double photoionization of CH2Cl2 at photon energies around the Cl 2p edge, were extracted from the shape and width of the experimentally obtained time-of-flight (TOF) distributions. The KERD spectra exhibit either smooth profiles or structures, depending on the moiety and photon energy. In general, the heavier the ionic fragments, the lower their average KERDs are. In contrast, the light H(+) fragments are observed with kinetic energies centered around 4.5-5.5 eV, depending on the photon energy. It was observed that the change in the photon energy involves a change in the KERDs, indicating different processes or transitions taking place in the breakup process. In the particular case of double ionization with the ejection of two charged fragments, the KERDs present have characteristics compatible with the Coulombic fragmentation model. Intending to interpret the experimental data, singlet and triplet states at Cl 2p edge of the CH2Cl2 molecule, corresponding to the Cl (2p → 10a1*) and Cl (2p → 4b1*) transitions, were calculated at multiconfigurational self-consistent field (MCSCF) level and multireference configuration interaction (MRCI). These states were selected to form the spin-orbit coupling matrix elements, which after diagonalization result in a spin-orbit manifold. Minimum energy pathways for dissociation of the molecule were additionally calculated aiming to give support to the presence of the ultrafast dissociation mechanism in the molecular breakup.

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Section: Results and Discussionsupporting

confidence: 92%

Section: Results and Discussionmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Kinetic Energy Release of the Singly and Doubly Charged Methylene Chloride Molecule: The Role of Fast Dissociation

Alcantara

Rocha

Gomes³

et al. 2016

J. Phys. Chem. A

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“…TIY spectra measured for CCl 3 SCN and CCl 2 FSCN near the Cl 2p region are depicted in Figure . The Cl 2p threshold is positioned in the region of 210.0 eV, in accordance with the values previously reported for similar molecules containing chlorinated groups. ,,− Centered at about 200.0, 202.0, and 204.0 eV, three wide and not well resolved bands can be observed in this region. Two of these signals could be attributed to electronic transitions related the spin–orbital split of the 2p term in the 2p 1/2 and 2p 3/2 levels of the excited species toward the LUMO+2 (σ* Cl–C ) vacant orbital.…”

Section: Resultssupporting

confidence: 87%

Electronic Properties and Dissociative Photoionization of Thiocyanates, Part III. The Effect of the Group’s Electronegativity in the Valence and Shallow-Core (Sulfur and Chlorine 2p) Regions of CCl₃SCN and CCl₂FSCN

et al. 2017

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Both photoelectron spectroscopy (PES) data and PhotoElectron-PhotoIon-Coincidence (PEPICO) spectra obtained from a synchrotron facility have been used to examine the electronic structure and the dissociative ionization of halomethyl thiocyantes in the valence and shallow-core S 2p and Cl 2p regions. Two simple and closely related molecules, namely, CClSCN and CClFSCN, have been analyzed to assess the role of halogen substitution in the electronic properties of thiocyanates. The assignment of the He(I) photoelectron spectra has been achieved with the help of quantum chemical calculations at the outer-valence Green's function (OVGF) level of approximation. The first ionization energies observed at 10.55 and 10.78 eV for CClSCN and CClFSCN, respectively, are assigned to ionization processes from the sulfur lone pair orbital [n(S)]. When these molecules are compared with CXSCN (X = H, Cl, F) species, a linear relationship between the vertical first ionization energy and electronegativity of CX group is observed. Irradiation of CClSCN and CClFSCN with photons in the valence energy regions leads to the formation of CClX and CClXSCN ions (X = Cl or F). Additionally, the achievement of the fragmentation patterns and the total ion yield spectra obtained from the PEPICO data in the S 2p and Cl 2p regions and several dissociation channels can be inferred for the core-excited species by using the triple coincidence PEPIPICO (PhotoElectron-PhotoIon-PhotoIon-Coincidence) spectra.

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“…They observed that the kinetic energy release of the CH 2 + ion presents a minimum at the Cl (2P 3/2 → 10a 1 *) resonance. Lu et al 8 observed that the CH 2 + ion yield presents a maximum at the Cl (2P 3/2 → 10a 1 *) resonance, which they interpreted as due to a fast dissociation through a highly repulsive potential curve. Alcantara et al 1 presented calculations of the potential curves in order to give support to this assertion.…”

Section: Introductionmentioning

confidence: 99%

Fragmentation of Valence and Core–Shell (Cl 2p) Excited C₂Cl₄ Molecule

et al. 2017

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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 CCl 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 CCl molecule, corresponding to the Cl(2p → 9b*) and Cl(2p → 8b*) 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.

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State-selective enhanced production of positive ions and excited neutral fragments of gaseous CH2Cl2following Cl
Kueih‐Tzu Lu
¹
,
J. M. Chen
²
,
J. M. Lee
³

et al.

Cited by 9 publications

References 52 publications

Kinetic Energy Release of the Singly and Doubly Charged Methylene Chloride Molecule: The Role of Fast Dissociation

Kinetic Energy Release of the Singly and Doubly Charged Methylene Chloride Molecule: The Role of Fast Dissociation

Electronic Properties and Dissociative Photoionization of Thiocyanates, Part III. The Effect of the Group’s Electronegativity in the Valence and Shallow-Core (Sulfur and Chlorine 2p) Regions of CCl₃SCN and CCl₂FSCN

Fragmentation of Valence and Core–Shell (Cl 2p) Excited C₂Cl₄ Molecule

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State-selective enhanced production of positive ions and excited neutral fragments of gaseous CH2Cl2following ClKueih‐Tzu Lu1, J. M. Chen2, J. M. Lee3 et al.

Cited by 9 publications

References 52 publications

Kinetic Energy Release of the Singly and Doubly Charged Methylene Chloride Molecule: The Role of Fast Dissociation

Kinetic Energy Release of the Singly and Doubly Charged Methylene Chloride Molecule: The Role of Fast Dissociation

Electronic Properties and Dissociative Photoionization of Thiocyanates, Part III. The Effect of the Group’s Electronegativity in the Valence and Shallow-Core (Sulfur and Chlorine 2p) Regions of CCl3SCN and CCl2FSCN

Fragmentation of Valence and Core–Shell (Cl 2p) Excited C2Cl4 Molecule

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State-selective enhanced production of positive ions and excited neutral fragments of gaseous CH2Cl2following Cl
Kueih‐Tzu Lu
¹
,
J. M. Chen
²
,
J. M. Lee
³

et al.

Electronic Properties and Dissociative Photoionization of Thiocyanates, Part III. The Effect of the Group’s Electronegativity in the Valence and Shallow-Core (Sulfur and Chlorine 2p) Regions of CCl₃SCN and CCl₂FSCN

Fragmentation of Valence and Core–Shell (Cl 2p) Excited C₂Cl₄ Molecule