Communication: Almost error-free resolution-of-the-identity correlation methods by null space removal of the particle-hole interactions

The Journal of Chemical Physics, 146, 211106 (2017);
The Journal of Chemical Physics, online article

We present a method to improve upon the resolution-of-the-identity (RI) for correlation methods. While RI is known to allow for drastic speedups, it relies on a cancellation of errors. Our method eliminates the errors introduced by RI which are known to be problematic for absolute energies. In this way, independence of the error compensation assumption for relative energies is also achieved. The proposed method is based on the idea of starting with an oversized RI basis and projecting out all of its unphysical parts. The approach can be easily implemented into existing RI codes and results in an overhead of about 30%, while effectively removing the RI error. In passing, this process alleviates the problem that for many frequently employed basis sets no optimized RI basis sets have been constructed. In this paper, the theory is presented and results are discussed exemplarily for the random phase approximation and Møller-Plesset perturbation theory.

TU München
Helmholtz München
MPI of Neurobiology
MPI of Biochemistry