Electron affinity of 7Li

Variationally optimized exponentially correlated Gaussian functions are employed to obtain nonrelativistic wave functions of the lithium atom and its negative ion. The energy levels are computed by means of the expansion in powers of the fine-structure constant alpha. The first term of this expansion corresponds to the nonrelativistic energy. The higher order terms represent the relativistic and radiative corrections and are determined by some effective Hamiltonians. Highly accurate expectation values of singular operators entering these Hamiltonians are computed using a set of expectation value identities. The resulting electron affinity of lithium atom 4984.96(18) cm(-1) agrees very well with 4984.90(17) cm(-1) of the latest measurements. (c) 2006 American Institute of Physics.