Core-to-valence spectroscopic detection of the CH{sub 2}Br radical and element-specific femtosecond photodissociation dynamics of CH{sub 2}IBr

Attar, Andrew R.; Piticco, Lorena; Leone, Stephen R.

doi:10.1063/1.4898375

Title: Core-to-valence spectroscopic detection of the CH{sub 2}Br radical and element-specific femtosecond photodissociation dynamics of CH{sub 2}IBr

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Abstract

Element-specific single photon photodissociation dynamics of CH{sub 2}IBr and core-to-valence absorption spectroscopy of CH{sub 2}Br radicals are investigated using femtosecond high-harmonic extreme ultraviolet (XUV) transient absorption spectroscopy. Photodissociation of CH{sub 2}IBr along both the C–I or C–Br reaction coordinates is observed in real-time following excitation at 266 nm. At this wavelength, C–I dissociation is the dominant reaction channel and C–Br dissociation is observed as a minor pathway. Both photodissociation pathways are probed simultaneously through individual 4d(I) N{sub 4/5} and 3d(Br) M{sub 4/5} core-to-valence transitions. The 3d(Br) M{sub 4/5} pre-edge absorption spectrum of the CH{sub 2}Br radical photoproduct corresponding to the C–I dissociation channel is characterized for the first time. Although the radical's singly occupied molecular orbital (SOMO) is mostly localized on the central carbon atom, the 3d(Br) → π{sup *}(SOMO) resonances at 68.5 eV and 69.5 eV are detected 2 eV below the parent molecule 3d(Br) → σ{sup *}(LUMO) transitions. Core-to-valence XUV absorption spectroscopy provides a unique probe of the local electronic structure of the radical species in reference to the Br reporter atom. The measured times for C–I dissociation leading to I and I{sup *} atomic products are 48 ± 12 fs and 44 ± 4 fs, respectively, whilemore »« less

Authors:

Attar, Andrew R.; Piticco, Lorena ^[1]; Leone, Stephen R. ^[1]

Department of Chemistry, University of California, Berkeley, California 94720 (United States)

Publication Date:: Tue Oct 28 00:00:00 EDT 2014

OSTI Identifier:: 22310750

Resource Type:: Journal Article

Journal Name:: Journal of Chemical Physics

Additional Journal Information:: Journal Volume: 141; Journal Issue: 16; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION SPECTRA; ABSORPTION SPECTROSCOPY; ATOMS; DETECTION; DISSOCIATION; ELECTRONIC STRUCTURE; EXCITATION; EXTREME ULTRAVIOLET RADIATION; MOLECULAR ORBITAL METHOD; MOLECULES; PHOTOLYSIS; RADICALS; RESONANCE; TIME RESOLUTION

Citation Formats


                    Attar, Andrew R., Piticco, Lorena, Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, Leone, Stephen R., Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, and Department of Physics, University of California, Berkeley, California 94720. Core-to-valence spectroscopic detection of the CH{sub 2}Br radical and element-specific femtosecond photodissociation dynamics of CH{sub 2}IBr.  United States: N. p., 2014. 
        Web.  doi:10.1063/1.4898375.

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                    Attar, Andrew R., Piticco, Lorena, Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, Leone, Stephen R., Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, & Department of Physics, University of California, Berkeley, California 94720. Core-to-valence spectroscopic detection of the CH{sub 2}Br radical and element-specific femtosecond photodissociation dynamics of CH{sub 2}IBr.  United States.  https://doi.org/10.1063/1.4898375

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                    Attar, Andrew R., Piticco, Lorena, Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, Leone, Stephen R., Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, and Department of Physics, University of California, Berkeley, California 94720. 2014.  
        "Core-to-valence spectroscopic detection of the CH{sub 2}Br radical and element-specific femtosecond photodissociation dynamics of CH{sub 2}IBr".  United States.  https://doi.org/10.1063/1.4898375.

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@article{osti_22310750,

  title        = {Core-to-valence spectroscopic detection of the CH{sub 2}Br radical and element-specific femtosecond photodissociation dynamics of CH{sub 2}IBr},

  author       = {Attar, Andrew R. and Piticco, Lorena and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 and Leone, Stephen R. and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 and Department of Physics, University of California, Berkeley, California 94720},

  abstractNote = {Element-specific single photon photodissociation dynamics of CH{sub 2}IBr and core-to-valence absorption spectroscopy of CH{sub 2}Br radicals are investigated using femtosecond high-harmonic extreme ultraviolet (XUV) transient absorption spectroscopy. Photodissociation of CH{sub 2}IBr along both the C–I or C–Br reaction coordinates is observed in real-time following excitation at 266 nm. At this wavelength, C–I dissociation is the dominant reaction channel and C–Br dissociation is observed as a minor pathway. Both photodissociation pathways are probed simultaneously through individual 4d(I) N{sub 4/5} and 3d(Br) M{sub 4/5} core-to-valence transitions. The 3d(Br) M{sub 4/5} pre-edge absorption spectrum of the CH{sub 2}Br radical photoproduct corresponding to the C–I dissociation channel is characterized for the first time. Although the radical's singly occupied molecular orbital (SOMO) is mostly localized on the central carbon atom, the 3d(Br) → π{sup *}(SOMO) resonances at 68.5 eV and 69.5 eV are detected 2 eV below the parent molecule 3d(Br) → σ{sup *}(LUMO) transitions. Core-to-valence XUV absorption spectroscopy provides a unique probe of the local electronic structure of the radical species in reference to the Br reporter atom. The measured times for C–I dissociation leading to I and I{sup *} atomic products are 48 ± 12 fs and 44 ± 4 fs, respectively, while the measured C–Br dissociation time leading to atomic Br is 114 ± 17 fs. The investigation performed here demonstrates the capability of femtosecond time-resolved core-level spectroscopy utilizing multiple reporter atoms simultaneously.},

  doi          = {10.1063/1.4898375},

  url          = {https://www.osti.gov/biblio/22310750},
  journal      = {Journal of Chemical Physics},

  issn         = {0021-9606},

  number       = 16,

  volume       = 141,

  place        = {United States},

  year         = {Tue Oct 28 00:00:00 EDT 2014},

  month        = {Tue Oct 28 00:00:00 EDT 2014}

}

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