CASSCF/CAS-PT2 study of hole transfer in stacked DNA nucleobases.

CASSCF and CAS-PT2 calculations are performed for the ground and excited states of radical cations consisting of two and three nucleobases. The generalized Mulliken-Hush approach is employed for estimating electronic couplings for hole transfer in the pi-stacks. We compare the CASSCF results with data obtained within Koopmans' approximation. The calculations show that an excess charge in the ground and excited states in the systems is quite localized on a single base both at the CASSCF level and in Koopmans' picture. However, the CASSCF calculations point to a larger degree of localization and, in line with this, smaller transition dipole moments. The agreement between the CAS-PT2 corrected energy gaps and the values estimated with Koopmans' theorem is better, with the CAS-PT2 calculations giving somewhat smaller gaps. Overall, both factors result in smaller CASSCF/CAS-PT2 couplings, which are reduced by up to 40% of the couplings calculated using Koopmans' approximation. The tabulated data can be used as benchmark values for the electronic couplings of stacked nucleobases. For the base trimers, comparison of the results obtained within two- and three-state models show that the multistate treatment should be applied to derive reliable estimates. Finally, the superexchange approach to estimate the donor acceptor electronic coupling in the stacks GAG and GTG is considered.