Series Expansion of a Scalable Hermitian Excitonic Renormalization Method

TL;DR

This paper introduces a Hermitian series expansion for a scalable excitonic renormalization method, improving accuracy and scalability in quantum chemistry calculations involving multiple fragments.

Contribution

It develops a Hermitian operator expansion that converges rapidly, enhancing the modularity and accuracy of excitonic renormalization for large systems.

Findings

Second-order method agrees with FCI for certain bond distances

Zeroth-order method comparable to CCSD(T) near equilibrium

Method scales efficiently to hundreds of fragments

Abstract

Utilizing the sparsity of the electronic structure problem, fragmentation methods have been researched for decades with great success, pushing the limits of ab initio quantum chemistry ever further. Recently, this set of methods was expanded to include a fundamentally different approach called excitonic renormalization, providing promising initial results. It builds a supersystem Hamiltonian in a second-quantized-like representation from transition-density tensors of isolated fragments, contracted with biorthogonalized molecular integrals. This makes the method fully modular in terms of the quantum chemical methods applied to each fragment and enables massive truncation of the state-space required. Proof-of-principle tests have previously shown that an excitonically renormalized Hamiltonian can efficiently scale to hundreds of fragments, but the ad hoc approach to building the Hamiltonian was not scalable to larger fragments. On the other hand, initial tests of the originally proposed modular Hamiltonian build, presented here, have shown the accuracy to be poor on account of its non-Hermitian character. In this study, we bridge the gap between these with an operator expansion that is shown to converge rapidly, tending towards a Hermitian Hamiltonian while retaining the modularity, yielding an accurate, scalable method. The accuracy is tested here for a beryllium dimer. At distances near equilibrium and longer, the zeroth-order method is comparable to CCSD(T), and the first-order method to FCI. The second-order method agrees with FCI for distances well up the inner repulsive wall of the potential. Deviations occurring at shorter bond distances are discussed along with approaches to scaling to larger fragments.