Cost-Effective Treatment of Scalar Relativistic Effects for Multireference Systems: A CASSCF Implementation Based on the Spin-free Dirac-Coulomb Hamiltonian.

Abstract

We present an implementation of the complete active space-self-consistent field (CASSCF) method specifically designed to be used in four-component scalar relativistic calculations based on the spin-free Dirac-Coulomb (SFDC) Hamiltonian. Our implementation takes full advantage of the properties of the SFDC Hamiltonian that allow us to use real algebra and to exploit point-group and spin symmetry to their full extent while including in a rigorous way scalar relativistic effects in the treatment. The SFDC-CASSCF treatment is more expensive than its non-relativistic counterpart only in the orbital optimization step, while exhibiting the same computational cost for the rate-determining full configuration interaction part. The numerical aspects are discussed, and the capabilities of the SFDC-CASSCF methodology are demonstrated through a pilot application.