Gas-phase reactions of An{sup +} and AnO{sub n}{sup +} [An = Th, U, Np, Pu, Am] with halogenated hydrocarbons [C{sub 14}F{sub 24}, C{sub 3}F{sub 6}, C{sub 2}H{sub 4}Cl{sub 2} and C{sub 2}H{sub 4}Br{sub 2}]

Gas-phase reactions of laser-ablated actinide metal and oxide ions, An{sup +} and AnO{sub 1,2}{sup +} (An = Th, U, Np, Pu, Am), with perfluorocarbons (C{sub 14}F{sub 24} and C{sub 3}F{sub 6}), 1,2-dichloroethane (C{sub 2}H{sub 4}Cl{sub 2}) and 1,2-dibromoethane (C{sub 2}H{sub 4}Br{sub 2}) were studied by laser ablation with prompt reaction and detection. A primary goal was to determine variations in reaction pathways within the region of the actinide series where a progression from d-block transition metal-like (e.g., Th{sup +}) to lanthanide-like (e.g., Am{sup +}) chemistry is manifested. The high stabilities of the actinide fluorides, AnF{sub x}{sup +} and AnOF{sub x}{sup +}, resulted in F-abstraction as the primary reaction channel with perfluorocarbons. The studied An exhibited discrepant proclivities towards F-abstraction which reflected variable oxidation state stabilities. Thus, Np produced Np{sup IV}F{sub 3}{sup +} and Np{sup V}OF{sub 2}{sup +} whereas oxidation of Am terminated at Am{sup III}F{sub 2}{sup +}. Reactions of An{sup +} with C{sub 2}H{sub 4}Cl{sub 2} produced exclusively AnCl{sub 1,2}{sup +} whereas reactions with C{sub 2}H{sub 4}Br{sub 2} produced both AnBr{sub 1,2}{sup +} and AnC{sub 2}H{sub 2}{sup +}. The distinctive appearance of dehydrobromination as a reaction pathway is interpreted in the context of organoactinide reaction mechanistics. Halogen abstraction reactions are of interest for assessing chemical manifestations of the changing oxidation behavior across the actinide series and may be of utility for post-ionization separation of actinides for purification or analysis. Also identified were directly ablated oxide cluster ions such as ThUO{sub 4}{sup +}, NpPuO{sub 3}{sup +} and U{sub 2}ThO{sub 7}{sup +} - their compositions and abundances are correlated with solid actinide oxide chemistry. (orig.)