Photodissociation of carbonic dibromide at 267 nm: Observation of three-body dissociation and molecular elimination of Br2

Xu, Duo; Huang, Jianhua; Francisco, Joseph S.; Hansen, Jaron C.; Jackson, William M.

doi:10.1063/1.1509063

Cited by 4 publications

(2 citation statements)

References 39 publications

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“…Rather, the angle between the transition dipole moment and the fragment recoil direction determines the degree of anisotropy. If there are more than one product channels, the angular distributions could be entirely different for different channels although they originate from a single electronic transition …”

Section: Discussionmentioning

confidence: 99%

Velocity Imaging Studies on Ion-Pair Dissociation of CH₃Br + hν_VUV → CH₃⁺ + Br^- as a Function of Wavelength

Huang

Price

et al. 2004

J. Phys. Chem. A

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The ion-pair dissociation dynamics of CH3Br + hνVUV → CH3 + + Br- as a function of vacuum ultraviolet (VUV) wavelength have been studied by means of velocity imaging. Photofragment excitation (PHOFEX) spectra as well as images for both the cation and the anion products have been collected, which confirm the dissociation occurs through the ion-pair channel from the momentum matching of both products. The wavelength region for the PHOFEX covers a small portion (from 121.4 to 122.7 nm) of the absorption spectrum where transitions from the ground state to both ns and np Rydberg states as well as to the underlying continuum states are all present. Images were taken at selected wavelengths both on the peaks and in the valleys of the PHOFEX spectrum, as well as at 118.22 nm. The PHOFEX spectra closely resemble the absorption spectra of CH3Br, and the images taken at peaks and continuum wavelengths in PHOFEX show no marked differences with respect to the product energy and angular distributions. These observations prompt us to conclude that the ion-pair state is directly populated by the VUV photons and the ion-pair dissociation is one of the major exit channels for the excited states in the energy region just below the ionization energy of the parent molecule, although large uncertainties in wavelength in the absorption spectra make the proposed mechanisms less conclusive.

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Section: Discussionmentioning

confidence: 99%

Velocity Imaging Studies on Ion-Pair Dissociation of CH₃Br + hν_VUV → CH₃⁺ + Br^- as a Function of Wavelength

Huang

Price

et al. 2004

J. Phys. Chem. A

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“…14 The analysis of the kinetic energy spectra yielded evidence for a concerted threebody decay and the formation of intermediate ClCO was found to be of minor importance in the Cl 2 CO dissociation process. 20 An asynchronously concerted three-body decay process was proposed to be responsible for formation of CO, Br͑ 2 P 3/2 ͒, and Br͑ 2 P 1/2 ͒. [15][16][17] A less abundant decay channel is the synchronously concerted mechanism, in which the two C-Cl bonds cleave in unison.…”

Section: Introductionmentioning

confidence: 99%

Photodissociation of phosgene: Theoretical evidence for the ultrafast and synchronous concerted three-body process

Qiu

Zhang

Shen

et al. 2009

The Journal of Chemical Physics

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The potential energy surfaces for Cl(2)CO dissociation into CO+Cl+Cl in the lowest two electronic singlet states (S(0) and S(1)) have been determined by the complete active space self-consistent field, coupled-cluster method with single and double excitations (CCSD), and equation-of-motion CCSD calculations, which are followed by direct ab initio molecular dynamics simulations to explore its photodissociation dynamics at 230 nm. It is found that the C-O stretching mode is initially excited upon irradiation and the excess internal energies are transferred to the C-Cl symmetric stretching mode within 200 fs. On average, the first and the second C-Cl bonds break completely within subsequent 60 and 100 fs, respectively. Electronic structure and dynamics calculations have thus provided a strong evidence that the photoinitiated dissociation of Cl(2)CO at 230 nm or shorter wavelengths is an ultrafast, adiabatic, and concerted three-body process. Since the two C-Cl bonds begin to break at the same time and the time interval between the two C-Cl bond broken fully is very short ( approximately 40 fs), the photoinitiated dissociation of Cl(2)CO to CO+2Cl can be considered as the synchronous concerted process.

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Investigation of 3-fragment photodissociation of O3 at 193.4 and 157.6 nm by coincident measurements

Ryazanov

Harrison

Wang

et al. 2014

The Journal of Chemical Physics

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Photodissociation of the ozone molecule at 193.4 nm (6.41 eV) and 157.6 nm (7.87 eV) is studied by fast-beam translational spectroscopy. Coincident detection of the dissociation products allows direct observation of the 3-fragment channel and determination of its kinematic parameters. The results indicate that at each wavelength, 3-fragment dissociation proceeds through synchronous concerted bond breaking, but the energy partitioning among the fragments is different. The branching fraction of the 3-fragment channel increases from 5.2(6)% at 193.4 nm to 26(4)% at 157.6 nm, in agreement with previous studies. It is shown that vibrational excitation of the symmetric stretch mode in O3 molecules created by photodetachment of O(3)(-) anion enhances the absorption efficiency, especially at 193.4 nm, but does not have a strong effect on the 3-fragment dissociation.

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Photodissociation of carbonic dibromide at 267 nm: Observation of three-body dissociation and molecular elimination of Br2

Cited by 4 publications

References 39 publications

Velocity Imaging Studies on Ion-Pair Dissociation of CH₃Br + hν_VUV → CH₃⁺ + Br^- as a Function of Wavelength

Velocity Imaging Studies on Ion-Pair Dissociation of CH₃Br + hν_VUV → CH₃⁺ + Br^- as a Function of Wavelength

Photodissociation of phosgene: Theoretical evidence for the ultrafast and synchronous concerted three-body process

Investigation of 3-fragment photodissociation of O3 at 193.4 and 157.6 nm by coincident measurements

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Photodissociation of carbonic dibromide at 267 nm: Observation of three-body dissociation and molecular elimination of Br2

Cited by 4 publications

References 39 publications

Velocity Imaging Studies on Ion-Pair Dissociation of CH3Br + hνVUV → CH3+ + Br- as a Function of Wavelength

Velocity Imaging Studies on Ion-Pair Dissociation of CH3Br + hνVUV → CH3+ + Br- as a Function of Wavelength

Photodissociation of phosgene: Theoretical evidence for the ultrafast and synchronous concerted three-body process

Investigation of 3-fragment photodissociation of O3 at 193.4 and 157.6 nm by coincident measurements

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Velocity Imaging Studies on Ion-Pair Dissociation of CH₃Br + hν_VUV → CH₃⁺ + Br^- as a Function of Wavelength

Velocity Imaging Studies on Ion-Pair Dissociation of CH₃Br + hν_VUV → CH₃⁺ + Br^- as a Function of Wavelength