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 closed-shell and open-shell dominant configurations correlating with the 4s(2) and 4s(1)3d(1) states of Ca, respectively. Unlike the neutral-ionic 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 π system: (i) a van der Waals complex with a doubly occupied highest molecular orbital, denoted Φ(2)(1), and a small negative charge on Ca and (ii) an open-shell singlet (biradical) at intermediate approach (Ca...C ≈2.5-2.7 Å) with molecular orbital structure (1)(2), where (2) is an orbital showing significant charge transfer form Ca to the π-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 has also been found; however, it does not necessarily represent the ground state at a given CaC 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-π complexes.