P. Depujo et al., CHEMILUMINESCENT CHANNELS IN REACTIONS OF BA(P-1(1)) WITH WATER, ALCOHOLS, AND ETHERS, The Journal of chemical physics, 99(4), 1993, pp. 2533-2540
The present paper investigates chemiluminescence in reactions of excit
ed barium atoms (6s6p P-1(1)) with water and a series of alcohols and
ethers. The electronically excited product molecule from the reaction
With H2O (and D2O) is BaOH (and BaOD) in the A 2PI, A' 2DELTA, and B2S
IGMA levels. The product molecule is always Ba-OR(x) in reactions with
alcohols ROH, whatever the size of the alcohol (methanol to butanol),
and whatever its class (primary to tertiary). By comparison, no chemi
luminescence was observed when the reactant was dimethyl and diallyl e
ther although allowed energetically. The nature of the product molecul
es in reaction with alcohols, and the absence of reaction with ethers
that were found here are remarkably close to what was found by Davis e
t al (submitted to J. Chem. Phys.) for the formation of ground state p
roducts in reactions of Ba(6s5d 1D2) with water, methanol, and dimethy
l ether. The present work thus allows us to extend the model of Davis
et al for the reactivity of Ba (6s5d 1D2) as a powerful and general de
scription of the reactivity of electronically excited barium atoms-the
close approach of excited barium to water or alkyl alcohol molecules
induces migration of the H atom that is bonded to oxygen. The reaction
and the nature of the reaction product is determined by the departure
of this H atom. The present paper also provides as side results deter
mination of the Ba-OCH3 binding energy 3.8 +/- 0.1 eV, and spectroscop
ic information on several barium monoalkoxides.