Beyond CCSD(T) Accuracy at Lower Scaling with Auxiliary Field Quantum Monte Carlo

• DOI: 10.1021/acs.jctc.4c01314
• Publication Date: 2025-02-05T11:38:56Z
• Authors: Ankit Mahajan; James H. Thorpe; Jo S. Kurian; David R. Reichman; Devin A. Matthews; Sandeep Sharma
• Keywords: Chemical Physics (physics.chem-ph); Condensed Matter - Strongly Correlated Electrons; Strongly Correlated Electrons (cond-mat.str-el); Physics - Chemical Physics; FOS: Physical sciences

We introduce a black-box auxiliary field quantum Monte Carlo (AFQMC) approach to perform highly accurate electronic structure calculations using configuration interaction singles and doubles (CISD) trial states. This method consistently provides more accurate energy estimates than coupled cluster singles and doubles with perturbative triples (CCSD(T)), often regarded as the gold standard in quantum chemistry. This level of precision is achieved at a lower asymptotic computational cost, scaling as $O(N^6)$ compared to the $O(N^7)$ scaling of CCSD(T). We provide numerical evidence supporting these findings through results for challenging main group and transition metal-containing molecules.<br/>19 pages, 13 figures<br/>