Isomers of NCO2: IR-absorption spectra of ONCO in solid Ne

Abstract

Irradiation of a Ne matrix sample containing NO and CO near 4 K with an ArF excimer laser at 193 nm yielded new lines at 2045.1 and 968.0 cm(-1) that were depleted upon secondary photolysis at 308 nm. These lines are assigned to C=O stretching and mixed stretching modes of ONCO, based on results of N-15-, C-13-, and O-18-isotopic experiments and quantum-chemical calculations. These calculations using density-functional theory (B3LYP and PW91PW91/aug-cc-pVTZ) predict five stable isomers of NCO2: ONCO, NCOO, N-cyc-CO2, CNOO, and cyc-CNOO, listed in order of increasing energy. According to B3LYP calculations, ONCO has a trans configuration, with bond angles of angle ONC congruent to 136.3 degrees and angle NOC congruent to 160.7 degrees. Calculated vibrational wave numbers, IR intensities, N-15-, C-13-, and O-18-isotopic shifts for ONCO agree satisfactorily with experimental results. ONCO was formed from reaction of CO with NO in its excited state. (c) 2005 American Institute of Physics.Irradiation of a Ne matrix sample containing NO and CO near 4 K with an ArF excimer laser at 193 nm yielded new lines at 2045.1 and 968.0 cm(-1) that were depleted upon secondary photolysis at 308 nm. These lines are assigned to C = O stretching and mixed stretching modes of ONCO, based on results of N-15-, C-13-, and O-18-isotopic experiments and quantum-chemical calculations. These calculations using density-functional theory (B3LYP and PW91PW91/aug-cc-pVTZ) predict five stable isomers of NCO2: ONCO, NCOO, N-cyc-CO2, CNOO, and cyc-CNOO, listed in order of increasing energy. According to B3LYP calculations, ONCO has a trans configuration, with bond angles of > ONC congruent to 136.3 degrees and > NOC congruent to 160.7 degrees. Calculated vibrational wave numbers, IR intensities, N-15-, C-13-, and O-18-isotopic shifts for ONCO agree satisfactorily with experimental results. ONCO was formed from reaction of CO with NO in its excited state.