Self-Interaction Corrected Functional Calculations of a Dipole-Bound Molecular Anion.

A self-interaction corrected density functional is used to describe the ground state of the CH3CN(-) ion that includes a dipole bound electron with large spatial extent and low binding energy. Without the correction, some commonly used density functionals based on the generalized gradient approximation as well as hybrid functionals fail to give a bound ground state of the anion. A negative HOMO orbital energy of magnitude 0.013 eV is obtained using the self-interaction corrected PBE functional in good correspondence with the experimentally estimated binding energy of 0.019 eV. The dipole bound electron polarizes the CH3CN molecule and increases its dipole moment by 7% to 4.2 D. Because the computational effort increases slowly with system size, as the number of electrons cubed, the results presented here point to a viable approach to theoretical studies of dipole bound electrons in large and complex systems such as molecular clusters, biological systems, and solvated electrons.