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Journal Article

Hard Numbers for Large Molecules: Toward Exact Energetics for Supramolecular Systems


Ambrosetti,  Alberto
Theory, Fritz Haber Institute, Max Planck Society;


Tkatchenko,  Alexandre
Theory, Fritz Haber Institute, Max Planck Society;

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Ambrosetti, A., Dario, A., DiStasio, R. A., & Tkatchenko, A. (2014). Hard Numbers for Large Molecules: Toward Exact Energetics for Supramolecular Systems. The Journal of Physical Chemistry Letters, 5(5), 849-855. doi:10.1021/jz402663k.

Cite as: http://hdl.handle.net/11858/00-001M-0000-0015-8755-B
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.