The Gas-Phase Kinetics of Reactions of Alkali Metal Atoms with Nitric Oxide

Abstract

Time-resolved atomic resonance absorption spectroscopy was employed, with flash-photolysis generation of atomic potassium and sodium at 734 K, to investigate the kinetics of K + NO + Ar and Na + NO + Ar. The low-pressure limit recombination rate constants are (1.0 ( 0.2) × 10 -31 and (1.9 ( 0.5) × 10 -32 cm 6 molecule -2 s -1 , respectively. Mainly ionic, triplet state adducts are predicted. RRKM modeling yielded K-NO and Na-NO bond dissociation enthalpies of 104 and 66 kJ mol -1 , which compare well with UQCISD(T)/6-311+ G(2d) ab initio values of 81 and 68 kJ mol -1 , respectively. For Li + NO +Ar, the predicted binding energy is 134 kJ mol -1 , which yields a predicted rate constant of 1.4 × 10 -31 cm 6 molecule -2 s -1 .

The Internal Rotation of Hydrogen Thioperoxide: Energy, Chemical Potential, and Hardness Profiles

“…Few papers have been published, most of them aimed at studying the molecular structure and gas-phase acidities and to characterize the thermochemistry of its radicals. 21,[24][25][26][27] HSOH presents two planar conformers, cis and trans, which are higher in energy with respect to the gauche stable conformation.…”