Beschreibung:
<jats:title>Abstract</jats:title><jats:p>Pulsed laser irradiation of solid potassium cyanide (KCN) produces, besides free nitrogen and carbon atoms, the molecular species KN and KC which are potential candidates for interstellar species of potassium. Additionally, N<jats:sub>3</jats:sub>, N<jats:sub>3</jats:sub><jats:sup>−</jats:sup>, KN<jats:sub>3</jats:sub>, C<jats:sub>3</jats:sub>, C<jats:sub>3</jats:sub><jats:sup>−</jats:sup>, and KC<jats:sub>3</jats:sub> are produced and isolated in solid noble gases as well as in solid N<jats:sub>2</jats:sub>. Molecular potassium nitrene (KN) reacts with dinitrogen in neon and argon matrices after photochemical excitation (<jats:italic>λ</jats:italic>=470 nm) forming molecular end‐on (<jats:italic>C</jats:italic><jats:sub>∞v</jats:sub>) and side‐on (<jats:italic>C</jats:italic><jats:sub>2v</jats:sub>) potassium azide isomers. The side‐on isomer (<jats:italic>C</jats:italic><jats:sub>2v</jats:sub>) is thermodynamically favored at the CCSD(T)/ma‐def2‐TZVP level of theory. It can be obtained from the end‐on isomer by UV‐irradiation (<jats:italic>λ</jats:italic>=273 nm).</jats:p>