PNNL

Abstract

The present paper illustrates key features of charge transfer between calcium atoms and prototype conjugated hydrocarbons (ethylene, benzene, and coronene) as elucidated by electronic structure calculations. One- and two-electron charge transfer is controlled by two sequential conical intersections. The two lowest electronic states that undergo a conical intersection have closedshell and open-shell dominant configurations correlating with the 4s2 and 4s13d1 states of Ca, respectively. Unlike the neutralionic state crossing in, for example, hydrogen halides or alkali halides, the path from separated reactants to the conical intersection region is uphill and the charge-transferred state is a biradical. The lowest-energy adiabatic singlet state shows at least two minima along a single approach path of Ca to the p system: (i) a van der Waals complex with a doubly occupied highest molecular orbital, denoted ?21 , and a small negative charge on Ca and (ii) an open-shell singlet (biradical) at intermediate approach (Ca?C distance ˜2.5–2.7 Å) with molecular orbital structure ?1?2, where ?2 is an orbital showing significant charge transfer form Ca to the p-system, leading to a one-electron multicentered bond. A third minimum (iii) at shorter distances along the same path corresponding to a closed-shell state with molecular orbital structure ?22 has also been found; however, it does not necessarily represent the ground state at a given Ca?C distance in all three systems. The topography of the lowest adiabatic singlet potential energy surface is due to the one- and two-electron bonding patterns in Ca-p complexes.