Molecular Anions Perspective

This Perspective attempts to shed light on developments in the theoretical and experimental study of molecular anions highlighting more recent workers in the field. The species I discuss include (i) valence-bound (singly and multiply charged) anions including atmospheric, catalytic, superhalogen, interfacial, and more; (ii) dipole- and correlation-bound anions including their role as doorways to other states and their appearance "in space", and (iii) metastable anions focusing on tools needed for their theoretical treatment. I also briefly discuss angular distributions of photodetached electrons and their growing utilization in experiments and theory. A recurring theme is the dependence of electron binding energies (EBEs) on the surrounding environment. Some anions that are nonexistent as isolated species evolve to be stable but with small EBEs when weakly solvated (e.g., as in a cluster or at an air-solvent interface). Others existing in isolation only as metastable species become stable when the underlying molecular framework contains one or more positively charged group (e.g., protonated side chains in a peptide) that generates a stabilizing Coulomb potential. On the other hand, a destabilizing Coulomb potential between/among negative sites in a multiply charged anion decreases the EBEs of each such site and generates a repulsive Coulomb barrier that can affect stability.