The polyatomic molecules SF6, BCl3, CF2Cl2, and SiF4 have been irradiated in the presence of H2 or N2 using intense focused CO2 laser pulses. All four of the polyatomic molecules underwent isotopically selective reactions showing depletion of the isotopic forms irradiated. The best enrichment was achieved with SF6; however, all systems showed similar behavior with regard to pressure and irradiation time. Both BCl3 and SiF4 showed evidence of isotopic rescrambling reactions that occurred on about a 1-h time scale. The mechanisms of the absorption process are believed to be enabled by the large density of states in the vibrational manifold of polyatomic molecules.
An increase in the ratio of S34/S32 of 3300% over its natural ratio has been obtained by irradiating SF6 in the presence of H2 with an intensely focused CO2 laser. The quantities of material separated are on the order of 100 μg.
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