Matrix photochemistry of nitrosyl chloride.: Interconversion of ClNO and ClON species by irradiation and tunneling effect Original Research Article

Natural and isotopic nitrosyl chloride (ClNO) isolated in nitrogen or argon matrices were irradiated with light at 266 nm. Weak absorption lines observed after photolysis were assigned to nitrogen hypochlorite (ClON). Spontaneous conversion of ClON into ClNO was observed and kinetic studies were consistent with a tunneling mechanism. Calculations using DFT and CCSD(T) were made for all isotopic species of each isomer. Energies, structures, harmonic vibrational wavelengths were calculated. Photoisomerization of ClNO into ClON as well as that of FNO into FON was also discussed.