Photoelectron Photoion Coincidence Spectroscopy of NCl3 and NCl2

Marius Gerlach; Sophie Monninger; Domenik Schleier; Patrick Hemberger; James T Goettel; Holger Braunschweig; Ingo Fischer

doi:10.1002/cphc.202100537

Photoelectron Photoion Coincidence Spectroscopy of NCl₃ and NCl₂

Chemphyschem. 2021 Nov 4;22(21):2164-2167. doi: 10.1002/cphc.202100537. Epub 2021 Aug 26.

Authors

Marius Gerlach¹, Sophie Monninger¹, Domenik Schleier¹, Patrick Hemberger², James T Goettel³, Holger Braunschweig³, Ingo Fischer¹

Affiliations

¹ Institute of Physical and Theoretical Chemistry, University of Würzburg, Am Hubland, 97074, Würzburg, Germany.
² Laboratory for Synchrotron Radiation and Femtochemistry, Paul Scherrer Institut (PSI), 5232, Villigen, Switzerland.
³ Institute of Inorganic Chemistry and Institute for Sustainable Chemistry and Catalysis with Boron, University of Würzburg, Am Hubland, 97074, Würzburg, Germany.

Abstract

We investigate NCl₃ and the NCl₂ radical by photoelectron-photoion coincidence spectroscopy using synchrotron radiation. The mass selected threshold photoelectron spectrum (ms-TPES) of NCl₃ is broad and unstructured due to the large geometry change. An ionization energy of 9.7±0.1 eV is estimated from the spectrum and supported by computations. NCl₂ is generated by photolysis at 213 nm from NCl₃ and its ms-TPES shows an extended vibrational progression with a 90 meV spacing that is assigned to the symmetric N-Cl stretching mode in the cation. An adiabatic ionization energy of 9.94 ± 0.02 eV is determined.

Keywords: nitrogen trichloride; photoelectron spectroscopy; photolysis; radicals; synchrotron radiation.

Abstract

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