Mail:
Dept. of Chemistry
Ohio State University
100 W. 18th Ave.
Columbus, OH 43210
Office:
412 CBEC
Email:
herbert@
chemistry.ohio-state.edu
This chapter provides a pedagogical review of basic theoretical concepts and electronic structure methods for the study of weakly-bound anions, cluster anions, solvated electrons, temporary anion resonances, and auto-ionizing excited-state resonances. Collectively, the author classifies these phenomena as systems exhibiting a loosely-bound electron. Thus, "loosely bound" might mean that the electron binding energy (vertical detachment energy) is small, but might also mean that there is an electron that it is only loosely associated with any particular molecular unit, even in cases where the electron binding energy is sizable. Basic terminology is defined and fundamental concepts are elucidated, and then the performance and appropriateness of various quantum-chemical models is discussed. Both wave function models and density functional theory are considered, and basis-set issues specific to loosely-bound electrons are discussed as well. Contact is made with numerous experimental results across a wide range of loosely-bound electron systems, including both gaseous and condensed-phase examples.