Local relativistic exact decoupling

We present a systematic hierarchy of approximations for local exact decoupling of four-component quantum chemical Hamiltonians based on the Dirac equation. Our ansatz reaches beyond the trivial local approximation that is based on a unitary transformation of only the atomic block-diagonal part of the Hamiltonian. Systematically, off-diagonal Hamiltonian matrix blocks can be subjected to a unitary transformation to yield relativistically corrected matrix elements. The full hierarchy is investigated with respect to the accuracy reached for the electronic energy and for selected molecular properties on a balanced test molecule set that comprises molecules with heavy elements in different bonding situations. Our atomic (local) assembly of the unitary exact-decoupling transformation— called local approximation to the unitary decoupling transformation (DLU)—provides an excellent local approximation for any relativistic exact-decoupling approach. Its order-N 2 scaling can be further reduced to linear scaling by employing a neighboring-atomic-blocks approximation. Therefore, DLU is an efficient relativistic method well suited for relativistic calculations on large molecules. If a large molecule contains many light atoms (typically hydrogen atoms), the computational costs can be further reduced by employing a well-defined nonrelativistic approximation for these light atoms without significant loss of accuracy. We also demonstrate that the standard and straightforward transformation of only the atomic block-diagonal entries in the Hamiltonian—denoted diagonal local approximation to the Hamiltonian (DLH) in this paper—introduces an error that is on the order of the error of second-order Douglas–Kroll–Hess (i.e., DKH2) when compared with exact-decoupling results. Hence, the local DLH approximation would be pointless in an exact-decoupling framework, but can be efficiently employed in combination with the fast to evaluate DKH2 Hamiltonian in order to speed up calculations for which ultimate accuracy is not the major concern. © 2012 American Institute of Physics .[ http://dx.doi.org/10.1063/1.4729788]