posted on 2015-12-17, 08:44authored byThomas-C. Jagau, Diep B. Dao, Nicholas
S. Holtgrewe, Anna I. Krylov, Richard Mabbs
Electron attachment to closed-shell
molecules is a gateway to various
important processes in the gas and condensed phases. The properties
of an electron-attached state, such as its energy and lifetime as
well as the character of the molecular orbital to which the electron
is attached, determine the fate of the anion. In this experimental
and theoretical study of copper and silver fluoride anions, we introduce
a new type of metastable anionic state. Abrupt changes in
photoelectron angular distributions point to the existence of autodetaching
states. Equation-of-motion coupled-cluster singles and doubles calculations
augmented by a complex absorbing potential identify some of these
states as Σ and Π dipole-stabilized resonances, a new
type of shape resonance. In addition, these molecules support valence
and dipole-bound states and a Σ resonance of charge-transfer
character. By featuring five different types of anionic states, they
provide a vehicle for studying fundamental properties of anions and
for validating new theoretical approaches for metastable states.