Photofragment imaging from mass-selected ions using a reflectron mass spectrometer. II: Formation mechanism of MgF+ in the photodissociation of Mg+FCH3 complex

Okutsu, Kenichi; Ohshimo, Keijiro; Hoshino, Hiroshi; Koyasu, Kiichirou; Misaizu, Fuminori

doi:10.1016/j.cplett.2015.04.023

Cited by 7 publications

(13 citation statements)

References 25 publications

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“…This SI-VMI instrument has similarities to other experiments described recently for photofragment imaging of mass-selected ions, − but it also has special features. The ions are not produced by photoionization, but instead grow directly in the laser vaporization process as they undergo cooling in a supersonic expansion.…”

Section: Methodsmentioning

confidence: 93%

Cation−π Complexes of Silver Studied with Photodissociation and Velocity-Map Imaging

2020

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Ag+(aromatic) ion–molecule complexes of benzene, toluene, or furan are generated in the gas phase by laser vaporization in a supersonic expansion. These ions are mass selected in a time-of-flight spectrometer and studied with ultraviolet laser photodissociation and photofragment imaging. UV laser excitation results in dissociative charge transfer (DCT) for these ions, producing neutral silver atom and the respective aromatic cation as the photofragments. Velocity-map imaging and slice imaging techniques are employed to investigate the kinetic energy release in these photodissociation processes. In each case, DCT produces significant kinetic energy, and evidence is also found for excitation of the internal rovibrational degrees of freedom for the molecular cations. Analysis of the kinetic energy release together with the known ionization energies of silver and the molecular ligands provides new information on the cation−π bond energies.

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Section: Methodsmentioning

confidence: 93%

Cation−π Complexes of Silver Studied with Photodissociation and Velocity-Map Imaging

2020

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“…Mainly three fragment ions (MgI + , ICH 3 + , and I + ) in addition to small amount of CH 3 + and Mg + fragment ions were observed in the TOF mass spectrum after the ultraviolet photodissociation of Mg + ICH 3 at 4.66 eV, as reported in the previous papers − by the authors. We here focused on the MgI + fragment ion, which showed a completely different dynamics with photofragment MgF + produced from photodissociation of Mg + FCH 3 …”

Section: Resultsmentioning

confidence: 99%

“…As mentioned above and in the previous reports, ,, pulsed high voltage (−2.0 kV, 0.6 μs width) was applied to the surface of the MCP detector. Therefore, an electrostatic field was created between the grounded surrounding flange parts and the MCP surface.…”

Section: Experimental and Theoretical Methodsmentioning

confidence: 91%

“…Details of the experimental setup were already described in the previous papers. ,, The present experimental apparatus consisted of a cluster ion source, a conventional angular-type reflectron TOF mass spectrometer (Jordan Co.) and a position-sensitive detector. The cluster ions consisting of Mg + and CH 3 I were produced by a pickup source .…”

Section: Experimental and Theoretical Methodsmentioning

confidence: 99%

“…The produced ions were detected by a linear time-of-flight (TOF) mass spectrometer, and both kinetic energy and angular distributions were measured simultaneously by a position-sensitive detector. Recently, ion imaging apparatuses were developed for observing the fragment ions produced from mass selected ions. − In our group, a reflectron TOF mass spectrometer combined with the position-sensitive detector for the photofragment ion imaging was used for the experiment. ,, …”

Section: Introductionmentioning

confidence: 99%

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Ion Imaging of MgI⁺ Photofragment in Ultraviolet Photodissociation of Mass-Selected Mg⁺ICH₃ Complex

et al. 2018

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We have observed images of MgI fragment ions produced in ultraviolet laser photodissociation of mass-selected MgICH ions at 266 nm. Split distribution almost perpendicular to the polarization direction of the photolysis laser was observed in the photofragment image. Potential energy curves of MgICH were obtained by theoretical calculations. Among these curves, the excited complex ion dissociated along almost repulsive potentials with several avoided crossings, which was connected to MgI + CH. In the ground state of MgICH, the CHI was bonded with Mg from the iodine side, and the Mg-I-C bond angle was calculated to be 101.1°. The theoretical results also indicated that the dissociation occurred after the 5A' ← 1A' photoexcitation, where the transition dipole moment was almost parallel to the Mg-I bond axis. The MgI and CH fragments dissociated each other parallel to the direction connecting those center-of-masses, which was 67° with respect to the transition dipole moment of 5A' ← 1A' photoexcitation. Therefore, the fragment recoil direction was assumed to approach perpendicular tendency against the polarization direction under the fast dissociation process. However, calculated potential energy curves showed a complicated reaction pathway for MgI production, including nonadiabatic processes, although the experimental results indicated the fast dissociation reaction.

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Photodissociation Spectroscopy and Photofragment Imaging of the Fe⁺(Acetylene) Complex

et al. 2023

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Tunable laser photodissociation spectroscopy in the 700−400 nm region and photofragment imaging experiments are employed to investigate the Fe + (acetylene) ion−molecule complex. At energies above a threshold at 679 nm, continuous dissociation is detected throughout the visible wavelength region, with regions of broad structure. Comparison to the spectrum predicted by time-dependent density functional theory (TD-DFT) indicates that the complex has a quartet ground state. The dissociation threshold for Fe + (acetylene) at 679 nm provides the dissociation energy on the quartet potential energy surface. Correction for the atomic quartet−sextet spin state energy difference provides an adiabatic dissociation energy of 36.8 ± 0.2 kcal/ mol. Photofragment imaging of the Fe + photoproduct produced at 603.5 nm produces significant kinetic energy release (KER). The photon energy and the maximum value of the KER provide an upper limit on the dissociation energy of D 0 ≤ 34.6 ± 3.2 kcal/mol. The dissociation energies determined from the spectroscopy and photofragment imaging experiments agree nicely with the value determined previously by collision-induced dissociation (38.0 ± 2.6 kcal/mol). However, both values are significantly lower than those produced by computational chemistry at the DFT level using different functionals recommended for transition-metal chemistry.

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Photofragment imaging from mass-selected ions using a reflectron mass spectrometer. II: Formation mechanism of MgF+ in the photodissociation of Mg+FCH3 complex

Cited by 7 publications

References 25 publications

Cation−π Complexes of Silver Studied with Photodissociation and Velocity-Map Imaging

Cation−π Complexes of Silver Studied with Photodissociation and Velocity-Map Imaging

Ion Imaging of MgI⁺ Photofragment in Ultraviolet Photodissociation of Mass-Selected Mg⁺ICH₃ Complex

Photodissociation Spectroscopy and Photofragment Imaging of the Fe⁺(Acetylene) Complex

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Photofragment imaging from mass-selected ions using a reflectron mass spectrometer. II: Formation mechanism of MgF+ in the photodissociation of Mg+FCH3 complex

Cited by 7 publications

References 25 publications

Cation−π Complexes of Silver Studied with Photodissociation and Velocity-Map Imaging

Cation−π Complexes of Silver Studied with Photodissociation and Velocity-Map Imaging

Ion Imaging of MgI+ Photofragment in Ultraviolet Photodissociation of Mass-Selected Mg+ICH3 Complex

Photodissociation Spectroscopy and Photofragment Imaging of the Fe+(Acetylene) Complex

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Product

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Ion Imaging of MgI⁺ Photofragment in Ultraviolet Photodissociation of Mass-Selected Mg⁺ICH₃ Complex

Photodissociation Spectroscopy and Photofragment Imaging of the Fe⁺(Acetylene) Complex