SFB 1309
Low-Scaling Self-Consistent Minimization of a Density Matrix Based Random Phase Approximation Method in the Atomic Orbital Space
2019-08-01
Daniel Graf, Matthias Beuerle, Christian Ochsenfeld
J. Chem. Theory Comput., 2019, 15, 8, 4468−4477
An efficient minimization of the random phase approximation (RPA) energy with respect to the one-particle density matrix in the atomic orbital space is presented. The problem of imposing full self-consistency on functionals depending on the potential itself is bypassed by approximating the RPA Hamiltonian on the basis of the well-known Hartree–Fock Hamiltonian making our self-consistent RPA method completely parameter-free. It is shown that the new method not only outperforms post-Kohn–Sham RPA in describing noncovalent interactions but also gives accurate dipole moments demonstrating the high quality of the calculated densities. Furthermore, the main drawback of atomic orbital based methods, in increasing the prefactor as compared to their canonical counterparts, is overcome by introducing Cholesky decomposed projectors allowing the use of large basis sets. Exploiting the locality of atomic and/or Cholesky orbitals enables us to present a self-consistent RPA method which shows asymptotically quadratic scaling opening the door for calculations on large molecular systems.
