eprintid: 1427811 rev_number: 34 eprint_status: archive userid: 608 dir: disk0/01/42/78/11 datestamp: 2014-04-25 19:14:40 lastmod: 2021-09-19 23:45:33 status_changed: 2014-04-25 19:14:40 type: article metadata_visibility: show item_issues_count: 0 creators_name: Ambrosetti, A creators_name: Alfe, D creators_name: Jr, DRA creators_name: Tkatchenko, A title: Hard Numbers for Large Molecules: Toward Exact Energetics for Supramolecular Systems ispublished: pub divisions: UCL divisions: B04 divisions: C06 divisions: F57 note: This document is the unedited Author’s version of a Submitted Work that was subsequently accepted for publication in Journal of Physical Chemistry Letters, copyright © American Chemical Society after peer review. To access the final edited and published work see http://dx.doi.org/10.1021/jz402663k abstract: Noncovalent interactions are ubiquitous in molecular and condensed-phase environments, and hence a reliable theoretical description of these fundamental interactions could pave the way toward a more complete understanding of the microscopic underpinnings for a diverse set of systems in chemistry and biology. In this work, we demonstrate that recent algorithmic advances coupled to the availability of large-scale computational resources make the stochastic quantum Monte Carlo approach to solving the Schrödinger equation an optimal contender for attaining “chemical accuracy” (1 kcal/mol) in the binding energies of supramolecular complexes of chemical relevance. To illustrate this point, we considered a select set of seven host–guest complexes, representing the spectrum of noncovalent interactions, including dispersion or van der Waals forces, π–π stacking, hydrogen bonding, hydrophobic interactions, and electrostatic (ion–dipole) attraction. A detailed analysis of the interaction energies reveals that a complete theoretical description necessitates treatment of terms well beyond the standard London and Axilrod–Teller contributions to the van der Waals dispersion energy. date: 2014-03-06 official_url: http://dx.doi.org/10.1021/jz402663k vfaculties: VMPS oa_status: green full_text_type: other language: eng primo: open primo_central: open_green verified: verified_manual elements_source: WoS-Lite elements_id: 940634 doi: 10.1021/jz402663k lyricists_name: Alfe, Dario lyricists_id: DALFE65 full_text_status: public publication: Journal of Physical Chemistry Letters volume: 5 number: 5 pagerange: 849 - 855 issn: 1948-7185 citation: Ambrosetti, A; Alfe, D; Jr, DRA; Tkatchenko, A; (2014) Hard Numbers for Large Molecules: Toward Exact Energetics for Supramolecular Systems. Journal of Physical Chemistry Letters , 5 (5) 849 - 855. 10.1021/jz402663k <https://doi.org/10.1021/jz402663k>. Green open access document_url: https://discovery.ucl.ac.uk/id/eprint/1427811/1/Hard_Numbers_for_Large_Molecules.pdf