Positron annihilation on large molecules

Positron annihilation on molecules is known to depend sensitively on molecular structure. For example, in the case of hydrocarbon molecules, modest changes in molecular size produce orders of magnitude changes in the observed annihilation rates. Although this process has been studied for more than three decades, many open questions remain. Experimental studies are described which are designed to test specific features of the annihilation process. Two possible mechanisms of the annihilation are considered theoretically: direct annihilation of the positron with one of the molecular electrons, including possible enhancement of this process when low-lying virtual or bound positron-molecule states are present, and resonant annihilation through positron capture into vibrationally excited states of the positron-molecule complex. The dependence of annihilation rates, λ, on positron temperature T_p is studied for the first time for molecules, and at low values of T_p the dependence follows a power law λ∝T^-ξ, with ξ≈0.5. These data are used to test the predictions of direct numerical calculations and theories of the virtual-level enhancement. Partially fluorinated hydrocarbons are studied in order to understand the rapid changes in annihilation rate produced in hydrocarbons as a result of fluorine substitution. These data are compared with the behavior expected due to direct annihilation when there is virtual or bound level enhancement. Measurements of positron annihilation on deuterated hydrocarbons are described which test the dependence of the annihilation on the nature of the molecular vibrations. The relationship of the presently available experimental data for annihilation in molecules to current theories of the annihilation process is discussed.