The synthesis of novel rare-gas compounds HXeCN, HXeNC, and HKrCN is r
eported. HKrCN represents the first stable compound with a Kr-C bond.
The novel molecules are formed in solid Xe and Kr by first photolyzing
monomeric HCN with a 193 nm ArF laser at 7.5 K. The photolysis produc
es isolated hydrogen atoms and CN radicals as evidenced by IR spectros
copy and laser induced fluorescence. Annealing of the Kr matrix at sim
ilar to 30 K and Xe matrix at similar to 50 K activates the hydrogen a
toms, and they react with rare-gas atoms surrounding the CN radicals p
roducing the rare-gas compounds, which are characterized in this work
by means of IR spectroscopy and ab initio calculations. Other products
observed are HNC and H2CN. Infrared induced photochemical conversion
of HXeNC to HXeCN is accomplished by exciting the Xe-H and C-N stretch
ing fundamentals of HXeNC. The existence of low barrier between these
two distinct isomers is confirmed by the ab initio calculations. (C) 1
998 American Institute of Physics.