Potential energy surfaces of charge transfer states

Abstract

ABSTRACT In this paper the potential energy curves of charge transfer (CT) electronic states and their interaction with local ones have been investigated. Besides the global view of these curves, special attention has been paid to the region of the crossing and the infinite separation limit. It was found that triple excitations are needed to accurately describe potential energy surfaces of CT states. Among the cheaper variants, both STEOM-CCSD and CCSD(T)(a)* methods are promising in this respect. The somewhat larger error of CCSD for CT states can be explained by its size extensivity error and the overestimation of the asymptotic excitation energy. Second order approximations are not advantageous for the error cancellation, in fact CC2 is much worse for CT states than any other method investigated here. The results also show that the location of the (avoided) crossings of local and CT states depend very much on the accurate description of the CT states. Failure to describe this topology might affect dynamics, and a warning, in particular in case of CC2, should be issued if CT states play a role in the physics of the problem.