MATRIX PHOTOCHEMISTRY OF NITROSYL CHLORIDE - INTERCONVERSION OF CLNO AND CLON SPECIES BY IRRADIATION AND TUNNELING EFFECT

Natural and isotopic nitrosyl chloride (ClNO) isolated in nitrogen or argon matrices were irradiated with light at 266 nm. Weak absorption l ines observed after photolysis were assigned to nitrogen hypochlorite (ClON). Spontaneous conversion of ClON into ClNO was observed and kine tic studies were consistent with a tunneling mechanism. Calculations u sing DFT and CCSD(T) were made for all isotopic species of each isomer . Energies, structures, harmonic vibrational wavelengths were calculat ed. Photoisomerization of ClNO into ClON as well as that of FNO into F ON was also discussed. (C) 1998 Elsevier Science B.V. All rights reser ved.