Showing papers by "Lester Andrews published in 1971"

Matrix Reactions of K and Rb Atoms with Oxygen Molecules

Abstract: Deposition of atomic beams of potassium and rubidium with oxygen molecules at high dilution in argon together on a salt window at 15°K produces the KO2 and RbO2 molecules, as identified by infrared spectra. Secondary reaction yields the KO2K and RbO2Rb molecules. Oxygen isotopic mixtures and simultaneous deposition of two different alkali‐metal atoms verify the molecular composition. Detailed concentration changes and oxygen isotropic mixtures identify the new molecular species O2KO2 and O2RbO2, the potassium and rubdium disuperoxide molecules which likely have the D2d structure. Force constants for the molecules synthesized here are compared with those reported earlier for LiO2 and NaO2.

Matrix Infrared Spectrum of OF and Detection of LiOF

Abstract: Simultaneous deposition of OF2 or 18OF2 diluted in argon with a beam of Li, Na, K, or Mg atoms on a salt window at 15°K produces new infrared absorptions which are due to the appropriate metal fluorides An intense absorption at 10286 cm−1 is independent of the metal used to generate the reaction, and this feature shows the appropriate oxygen‐18 shift for assignment to the OF free radical Additional bands show a metal dependence and are attributed to weakly bonded MF···OF dimers Use of isotopic mixtures shows that bands at 7140 and 4175 cm−1 using 6Li are due to a new species containing single lithium and oxygen atoms which concentration studies suggest to be the molecule LiOF

Argon Matrix Infrared Spectrum of the ClO Radical

Abstract: The matrix reaction of dichlorine monoxide with alkali metal atoms at high dilution in argon produces absorptions due to the appropriate alkali metal chlorides and bands near 995 and 850 cm−1 which show the calculated oxygen isotopic shift for a ClO diatomic species and are independent of the alkali metal used to generate the reaction. The 995‐cm−1 feature has an appropriate chlorine isotopic counterpart for ClO. Experiments altering the concentrations of Cl2O and lithium atom reactants identify the 995‐cm−1 absorption as the vibrational fundamental of ClO and the 850‐cm−1 band as ClO perturbed by another molecule, perhaps the Cl2O precursor. This assignment is consistent with the conclusions of earlier matrix isolation studies of ClO species. The high Cl–O force constant in the chlorine oxide free radical is rationalized in terms of (p–p) π bonding.