%0 Journal Article
%@ 1948-7185
%A Ambrosetti, A
%A Alfe, D
%A Jr, DRA
%A Tkatchenko, A
%D 2014
%F discovery:1427811
%J Journal of Physical Chemistry Letters
%N 5
%P 849 - 855
%T Hard Numbers for Large Molecules: Toward Exact Energetics for Supramolecular Systems
%U https://discovery.ucl.ac.uk/id/eprint/1427811/
%V 5
%X 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.
%Z 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