Improving Perturbation Theory with the Sum-of-Squares: Third Order

Abstract: The sum-of-squares method can give rigorous lower bounds on the energy of quantum Hamiltonians. Unfortunately, typically using this method requires solving a semidefinite program, which can be computationally expensive. Further, the typically used degree-$4$ sum-of-squares (also known as the 2RDM method) does not correctly reproduce second order perturbation theory. Here, we give a general method, an analogue of Wigner's $2n+1$ rule for perturbation theory, to compute the order of the error in a given sum-of-squares ansatz. We also give a method for finding solutions of the dual semidefinite program, based on a perturbative ansatz combined with a self-consistent method. As an illustration, we show that for a class of model Hamiltonians (with a gap in the quadratic term and quartic terms chosen as i.i.d. Gaussians), this self-consistent sum-of-squares method significantly improves over the 2RDM method in both speed and accuracy, and also improves over low order perturbation theory. We then explain why the particular ansatz we implement is not suitable for use for quantum chemistry Hamiltonians (due to presence of certain large diagonal terms), but we suggest a modified ansatz that may be suitable, which will be the subject of future work.