Electron affinity of Li: A state-selective measurement

We have investigated the threshold of photodetachment of Li^- leading to the formation of the residual Li atom in the $2p ^2P$ state. The excited residual atom was selectively photoionized via an intermediate Rydberg state and the resulting Li^+ ion was detected. A collinear laser-ion beam geometry enabled both high resolution and sensitivity to be attained. We have demonstrated the potential of this state selective photodetachment spectroscopic method by improving the accuracy of Li electron affinity measurements an order of magnitude. From a fit to the Wigner law in the threshold region, we obtained a Li electron affinity of 0.618 049(20) eV.