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In this study, we employ benchmark diffusion quantum Monte Carlo (DMC) methods to investigate the relative energies and role of electron correlation on a set of adenine dimer conformations generated via a search of the potential energy landscape using the global optimizer algorithm. Relative DMC energies are compared against a wide range of density functional theory (DFT) approximation results. We find that although most of the DFT functionals perform well for low-energy structures, their accuracy varies significantly for higher-energy conformations, including stacked and T-shaped structures. A large fraction of the variation is due to the treatment of the van der Waals interaction. BLYP, B3LYP, and PBE0 significantly improve with added D4 dispersion, while the recent r2SCAN-D4 and \u03c9B97M-V functionals show the least scatter and closest agreement with the DMC. These findings highlight the delicate nature of these interactions in biomolecular systems and provide guidance for simulations of their structure and dynamics and for the development of machine learned interatomic potentials.<\/jats:p>","DOI":"10.1063\/5.0332651","type":"journal-article","created":{"date-parts":[[2026,8,7]],"date-time":"2026-08-07T13:48:18Z","timestamp":1786110498000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":0,"title":["Role of electron correlation on the adenine dimer interaction for non-equilibrium geometries: A benchmark quantum Monte Carlo study"],"prefix":"10.1063","volume":"165","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-2417-9335","authenticated-orcid":false,"given":"L.","family":"Washburn","sequence":"first","affiliation":[{"name":"Biosciences Division, Oak Ridge National Laboratory 1 , Oak Ridge, Tennessee 37831,","place":["USA"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8233-3057","authenticated-orcid":false,"given":"A.","family":"Sedova","sequence":"additional","affiliation":[{"name":"Biosciences Division, Oak Ridge National Laboratory 1 , Oak Ridge, Tennessee 37831,","place":["USA"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5539-4017","authenticated-orcid":false,"given":"P. 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