Journal of Chemical Physics, Vol.105, No.6, 2153-2160, 1996
Matrix-Isolation Study of the Interaction of Excited Neon Atoms with O-3 - Infrared-Spectrum of O-3(-) and Evidence for the Stabilization of O-2-Center-Dot-Center-Dot-Center-Dot-O-4(+)
When a Ne:O-3 sample is codeposited at approximately 5 K with neon atoms that have been excited in a microwave discharge, the most prominent infrared absorptions of the resulting solid are contributed by trans- and cyc-O-4(+) and by O-3(-). The failure to detect infrared absorptions of O-3(+) is consistent with the initial formation of that species in one or more dissociative excited states. The nu(3) absorption of O-3(-) appears at 796.3 cm(-1), close to its position in earlier argon-matrix experiments in which photoionization of an alkali metal atom provided the electron source and in which diffusion of the atomic cation would result in the stabilization of appreciable M(+)O(3)(-). The identification of O-3(-) isolated in solid neon is supported by observations of O-3(-) generated from isotopically substituted Ne:O-2:N2O samples, also codeposited with excited neon atoms. An upper bound of 810 cm(-1) is estimated for the gas-phase band center of nu(3) of O-3(-). Infrared absorptions which grow on mild warmup of the sample are tentatively assigned to an O-2 ... O-4(+) complex.
Keywords:POTENTIAL-ENERGY SURFACES;COUPLED-CLUSTER METHOD;SOLID NEON;VIBRATIONAL-SPECTRA;ARGON MATRIX;PHOTOELECTRON-SPECTROSCOPY;PHOTO-DISSOCIATION;ELECTRONIC STATES;OZONE CATION;IONS