Multireference quantum chemistry through a joint density matrix renormalization group and canonical transformation theory

We describe the joint application of the density matrix renormalization group and canonical transformation theory to multireference quantum chemistry. The density matrix renormalization group provides the ability to describe static correlation in large active spaces, while the canonical transformation theory provides a high-order description of the dynamic correlation effects. We demonstrate the joint theory in two benchmark systems designed to test the dynamic and static correlation capabilities of the methods, namely, (i) total correlation energies in long polyenes and (ii) the isomerization curve of the [ Cu 2 O 2 ] 2 + core. The largest complete active spaces and atomic orbital basis sets treated by the joint DMRG-CT theory in these systems correspond to a ( 24 e , 24 o ) active space and 268 atomic orbitals in the polyenes and a ( 28 e , 32 o ) active space and 278 atomic orbitals in [ Cu 2 O 2 ] 2 + .