## Photoelectron Photoion Coincidence Spectroscopy of NCl$$_{3}$$ and NCl$$_{2}$$

Please always quote using this URN: urn:nbn:de:bvb:20-opus-257322
• We investigate NCl$$_{3}$$ and the NCl$$_{2}$$ radical by photoelectron-photoion coincidence spectroscopy using synchrotron radiation. The mass selected threshold photoelectron spectrum (ms-TPES) of NCl$$_{3}$$ 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 NCl$$_{3}$$ and its ms-TPES shows an extended vibrational progression with a 90 meV spacing that is assigned to the symmetric N−ClWe investigate NCl$$_{3}$$ and the NCl$$_{2}$$ radical by photoelectron-photoion coincidence spectroscopy using synchrotron radiation. The mass selected threshold photoelectron spectrum (ms-TPES) of NCl$$_{3}$$ 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 NCl$$_{3}$$ 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.