Spectroscopy of molecular ions: Laser-induced fragmentation spectra of COS+, A2Π ← X2Π and B2Σ ← X2Π

Kakoschke, R.; Boesl, U.; Hermann, Jakob; Schlag, E. W.

doi:10.1016/0009-2614(85)85369-0

Cited by 33 publications

(12 citation statements)

References 21 publications

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“…1, the two spinorbit components ͑0,0,0͒ A 2 ⌸ 3/2 and ͑0,0,0͒ A 2 ⌸ 1/2 are completely resolved. 29 We note that the spin-orbit splitting for OCS ϩ (A 2 ⌸ 3/2,1/2 ) is more than threefold smaller than the value of 367 cm Ϫ1 for the OCS ϩ (X 2 ⌸) ground state. These IEs for OCS ϩ (A 2 ⌸ 3/2,1/2 ) are in excellent agreement with previous determinations by other methods 10,16,19,31 as shown by the comparison given in Table IV.…”

Section: A Ocs ¿ "A 2 ⌸…mentioning

confidence: 62%

Vacuum ultraviolet pulsed field ionization-photoelectron study of OCS in the energy range of 15–19 eV

Chen

Hochlaf²,

Rosmus³

et al. 2002

The Journal of Chemical Physics

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Pulsed field ionization-photoelectron bands for CO 2 + (A 2 Π u and B 2 Σ u + ) in the energy range of 17.2-19.0 eV: An experimental and theoretical study High resolution pulsed field ionization-photoelectron study of CO 2 + (X 2 Π g ) in the energy range of 13.6-14.7 eV J.Vacuum ultraviolet pulsed field ionization-photoelectron ͑PFI-PE͒ spectra for OCS have been obtained in the energy range 15.0-19.0 eV, covering the vibronic bands of OCS ϩ ͑A 2 ⌸, B 2 ⌺ ϩ , and C 2 ⌺ ϩ ͒. The ionization energies for the formation of the ground vibrational levels of OCS ϩ (A 2 ⌸ 3/2 , A 2 ⌸ 1/2 , B 2 ⌺ ϩ , and C 2 ⌺ ϩ ͒ from the ground OCS(X 1 ⌺ ϩ ) state have been determined as 15.0759Ϯ0.0005 eV, 15.0901Ϯ0.0005 eV, 16.0403Ϯ0.0005 eV, and 17.9552Ϯ0.0005 eV, respectively. We have also generated the theoretical adiabatic three dimensional potential energy functions ͑PEFs͒ for OCS ϩ (A 2 ⌸) by employing the complete active space self-consistent field and internally contracted multireference configuration interaction methods. Using these PEFs, the spectroscopic constants and low-lying rovibronic energy levels for OCS ϩ (A 2 ⌸) are calculated variationally. These calculations have made possible the identification of many PFI-PE vibronic bands for OCS ϩ (A 2 ⌸), which are originated from vibronic and Fermi resonance interactions. Owing to the different equilibrium geometries between the OCS ϩ (A 2 ⌸) and OCS(X 1 ⌺ ϩ ) states, the PFI-PE spectrum for OCS ϩ (A 2 ⌸) exhibits a long vibronic progression extending well above the OCS ϩ (B 2 ⌺ ϩ ) state. On the contrary, the PFI-PE spectra for OCS ϩ ͑B 2 ⌺ ϩ and C 2 ⌺ ϩ ͒ are overwhelmingly dominated by the ground ͑0,0,0͒ bands, exhibiting only weak vibrational progressions.

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Section: A Ocs ¿ "A 2 ⌸…mentioning

confidence: 62%

Vacuum ultraviolet pulsed field ionization-photoelectron study of OCS in the energy range of 15–19 eV

Chen

Hochlaf²,

Rosmus³

et al. 2002

The Journal of Chemical Physics

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“…47 meV, 368 cm Ϫ1 ͒ in good agreement with that deduced from analysis of the OCS ϩ (ÃϪX) laser induced fluorescence ͑LIF͒ [27][28][29] and the laser induced fragmentation spectra of OCS ϩ . 30 Frequencies for the ground state ion stretching vibrations are well established: 1 ϳ2080 cm Ϫ1 and 3 ϳ698 cm…”

Section: Introductionmentioning

confidence: 99%

Resonance enhanced multiphoton ionization spectroscopy of carbonyl sulphide

Morgan

Orr‐Ewing

Ascenzi

et al. 1996

The Journal of Chemical Physics

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Rydberg excited states of the OCS molecule in the energy range 70500-86000 cm Ϫ1 have been investigated via the two and three photon resonance enhancements they provide in the mass resolved multiphoton ionization ͑MPI͒ spectrum of a jet-cooled sample of the parent molecule. Spectral interpretation has been assisted by companion measurements of the kinetic energies of the photoelectrons that accompany the various MPI resonances. The present study supports the earlier conclusions of Weinkauf and Boesl ͓J. Chem. Phys. 98, 4459 ͑1993͔͒ regarding five Rydberg origins in the 70500-73000 cm Ϫ1 energy range, attributable to, respectively, states of 3 ⌸, 1 ⌸, 3 ⌬, 1 ⌬ and 1 ⌺ ϩ symmetry arising from the 4p←3 orbital promotion. We also identify a further 21 Rydberg origins at higher energies. These partition into clumps with quantum defects ca. 3.5 and 4.5, which we associate with the orbital promotions np←3 (nϭ5,6), and others with near integer quantum defect which are interpretable in terms of excitation to s,d and ͑possibly͒ f Rydberg orbitals. We also identify MPI resonances attributable to CO(X 1 ⌺ ϩ ) fragments and to S atoms in both their ground ( 3 P) and excited ( 1 D) electronic states. Analysis of the former resonances confirms that the CO(X) fragments resulting from one photon dissociation of OCS at excitation wavelengths ca. 230 nm are formed with a highly inverted, bimodal rotational state population distribution, whilst the latter are consistent with previous reports of the wavelength dependence for forming ground and excited state S atoms in the near uv photolysis of OCS.

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“…[14][15][16][17] Figure 2b displays a photofragment (S + ) yield spectrum when the predissociation laser wavelength (λ 2 ) was scanned with the ionization laser (λ 1 ) fixed at the peak of the F ˜1∆ 0 0 0 transition, as indicated by the arrow in Figure 2a. On the basis of known vibrational frequencies, 13,18 all spectral features can be assigned to the X ˜2∏ f B ˜2 ∑ vibronic transitions of OCS + . For clarity, only the four transitions reported here in acquiring the fragment-ion images are labeled.…”

Section: Resultsmentioning

confidence: 99%

“…1/2 f B ˜2∑ + vibronic transition. 13 The predissociated product ion S + was then probed using a time-sliced velocity imaging technique. A fast high-voltage switch (∼30 ns duration) was pulsed to gate the gain of the Chevron-type microchannel plate (MCP) for mass selection as well as the time slicing of the ion packet.…”

Section: Methodsmentioning

confidence: 99%

Imaging the Mode-Selected Predissociation of OCS⁺[(v₁v₂v₃)B̃²Σ⁺]

2005

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A new experimental approach to explore the mode-selected chemistry is proposed and demonstrated here. In this approach a double-resonance excitation scheme is exploited to prepare a well-defined mode or state of a parent ion. A time-sliced velocity imaging technique interrogates the fragment ion from the subsequent predissociation. Application to the title process reveals remarkable mode-specific behaviors despite the long dissociation time associated with the indirect bond-breaking process. A qualitative interpretation of the major findings is surmised.

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Spectroscopy of molecular ions: Laser-induced fragmentation spectra of COS+, A2Π ← X2Π and B2Σ ← X2Π

Cited by 33 publications

References 21 publications

Vacuum ultraviolet pulsed field ionization-photoelectron study of OCS in the energy range of 15–19 eV

Vacuum ultraviolet pulsed field ionization-photoelectron study of OCS in the energy range of 15–19 eV

Resonance enhanced multiphoton ionization spectroscopy of carbonyl sulphide

Imaging the Mode-Selected Predissociation of OCS⁺[(v₁v₂v₃)B̃²Σ⁺]

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Spectroscopy of molecular ions: Laser-induced fragmentation spectra of COS+, A2Π ← X2Π and B2Σ ← X2Π

Cited by 33 publications

References 21 publications

Vacuum ultraviolet pulsed field ionization-photoelectron study of OCS in the energy range of 15–19 eV

Vacuum ultraviolet pulsed field ionization-photoelectron study of OCS in the energy range of 15–19 eV

Resonance enhanced multiphoton ionization spectroscopy of carbonyl sulphide

Imaging the Mode-Selected Predissociation of OCS+[(v1v2v3)B̃2Σ+]

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Imaging the Mode-Selected Predissociation of OCS⁺[(v₁v₂v₃)B̃²Σ⁺]