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oe1(光电查) - 科学论文

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?? 中文(中国)
  • Resonance enhanced multiphoton ionisation (REMPI) detection of Cl( <sup>2</sup> P <sub/>j</sub> ) atom in the photodissociation of halogenated pyrimidines at 235 nm: role of triplet states

    摘要: The dynamics of chlorine atom (2Pj) formation in the photodissociation process of halogen substituted pyrimidines, namely, 2,4,6-trichloropyrimidine and 5-chloro-2,4,6-trifluoropyrimidine have been studied around 235 nm using Resonance Enhanced Multiphoton Ionisation Time-of-Flight Mass Spectrometry technique. For the chlorine atom dissociation channel, we have determined the translational energy distribution, the recoil anisotropy parameter, β, and the spin–orbit branching ratio. In both the molecules, the TOF profiles for Cl (2P3/2) and Cl* (2P1/2) are found to be independent of laser polarisation suggesting a zero value for β, within the experimental uncertainties. For 2,4,6-trichloropyrimidine, the average translational energies for Cl and Cl* elimination channels are determined to be 6.0 ± 1.2 and 7.0 ± 1.5 kcal/mol, respectively. Similarly, for 5-chloro-2,4,6-trifluoropyrimidine, the average translational energies for Cl and Cl* elimination channels are determined to be 6.5 ± 1.2 and 7.9 ± 1.6 kcal/mol, respectively. Computational calculations are performed to generate the potential energy curves along the dissociating C-Cl bond using equation of motion coupled cluster with single and double excitations (EOM-CCSD) method. Computational studies suggest the role of triplet states in the photodissociation process forming the Cl atom.

    关键词: REMPI-TOF,halogenated pyrimidines,translational energy,spin-orbit ratio,Photodissociation dynamics

    更新于2025-09-23 15:23:52

  • Bimodal velocity distributions in the photodesorption of CO from Si(1 0 0) suggest V-to-T energy transfer

    摘要: The photodesorption of CO from Si(1 0 0) has been studied using 355 and 266 nm light obtaining time-of-flight spectra detailing the translation energy released. The spectra clearly exhibit two non-thermal desorption channels, of which one is characterized by an offset energy the size of which is remarkably close to the vibrational quantum of CO. Detailed studies of the spectra as function of coverage and laser fluence used prove that both desorption channels originate from a single adsorbed species. It is suggested that the energy offset is due to vibrational to translational energy transfer along the reaction pathway of the desorbing molecule.

    关键词: Photodesorption,Time-of-flight spectra,Vibrational to translational energy transfer,CO,Si(1 0 0)

    更新于2025-09-11 14:15:04