Molecular properties via a subsystem density functional theory formulation: A common framework for electronic embedding

Recently, a general framework suitable for general frozen-density embedding (FDE) methods was published [S. Höfener, A. S. P. Gomes, and L. Visscher, J. Chem. Phys. 136, 044104 (2012)]10.1063/1.3675845. In the present article, we report the fragmentation of a supermolecule while treating all subsystems with coupled-cluster theory and the interaction of the subsystems with density-functional theory. This variant is denoted wave-function theory in wave-function theory FDE, or coupled-cluster theory in coupled-cluster theory FDE. Main target of this approach is not the embedding of a single molecule in large solvation shells, but rather the possibility to divide a complex system consisting of several molecules when all subsystems are to be treated with, e.g., coupled-cluster methods to provide a balanced and unbiased description. We present numerical results for hydrogen-bonded complexes which exhibit rather strong interactions. Cases with weakly interacting subsystems are expected to exhibit even higher accuracy. This facilitates the study of properties of larger complexes such as DNA base pairs with coupled-cluster methods. © 2012 American Institute of Physics