THE INFRARED SPECTRUM OF H2O2+H_{2}O_{2}^{+} TRAPPED IN SOLID NEON

Author Institution: Optical Technology Division, National Institute of Standards and TechnologyWhen a $Ne:H_{2}O_{2}^{+}$ sample is codeposited at approximately 5 K with a beam of microwave-excited neon atoms, photoionization and Penning ionization of the $H_{2}O_{2}$ leads to the stabilization of the $H_{2}O_{2}^{+}$ cation. Although the energy of the excited neon atoms exceeds that required that required for the formation of $HO_{2}^{+}$ from $H_{2}O_{2}^{+}$, as has been previously found in photonization studies, the yield of this fragment ion is small. The infrared spectra observed for $H_{2}O_{2}^{+}$ and for the deuterium-substituted isotopomers will be compared with those predicted by ab initio calculations

THE VIBRATIONAL SPECTRA OF MOLECULAR IONS FORMED FROM HBr AND HI AND TRAPPED IN SOLID NEON

Author Institution: National Institute of Standards and Technology, Gaithersburg, MD 20899.When a Ne:HBr or a Ne:HI sample is codeposited at 5 K with a beam of neon atoms that has been excited by a microwave discharge, the solid deposit shows prominent infrared infrared absorptions of the $HX^{+}, {(HX)_{2}}^{+}$, and $XHX^{-}$ ion products. The vibrational spectra of these species and their behavior on subsequent exposure of the deposit to various ranges of visible and ultraviolet radiation are compared with the corresponding properties previously observed for Ne:HCl samples

INFRARED SPECTRUM OF O3−O_{3}^{-} ISOLATED IN SOLID NEON AND EVIDENCE FOR THE STABILIZATION OF O2⋯O4+O_{2}\cdots{O}_{4}^{+}

Author Institution: Molecular Physics Division, National Institute of Standards and TechnologyWhen 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:$O_{2}:N_{2}O$ 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 $O_{2}\cdots{O}_{4}^{+}$ complex

INFRARED SPECTRA OF MOLECULAR IONS FORMED FROM PF3PF_{3} AND PF5PF_{5} AND TRAPPED IN A NEON MATRIX

Author Institution: Optical Technology Division, National Institute of Standards and Technology; Physical and Chemical Properties Division, National Institute of Standards and TechnologyWhen $PF_{3}$ or $PF_{5}$ is subjected to Penning ionization and photoionization by excited neon atoms and their resonance radiation (16.6-16.8 eV) and the products are rapidly frozen in an excess of solid neon, the resulting solid deposit shows prominent infrared absorptions which can be assigned to cation and anion products, including $PF_{3}^{+}, PF_{4}^{+}$ and $PF_{4}^{+}$. Because phosphorus and fluorine each possess only one stable isotope, consideration of the spectra of related systems and of the results of ab initio calculations is important in making spectral assignments. Processes which lead to the stabilization of the observed ionic species will be discussed