Article (Scientific journals)
Hard numbers for large molecules: Toward exact energetics for supramolecular systems
Ambrosetti, A.; Alfè, D.; Distasio, R. A. et al.
2014In Journal of Physical Chemistry Letters, 5 (5), p. 849-855
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Keywords :
Monte Carlo; Schrödinger equation; Dinger equation; Electrostatic attractions; Hydrophobic interactions; Non-covalent; Van der waals; Binding energy; Cationic surfactants; Dispersions; Hydrogen bonds; Hydrophobic chromatography; Hydrophobicity; Ions; Monte Carlo methods; Van der Waals forces; Supramolecular chemistry
Abstract :
[en] 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. © 2014 American Chemical Society.
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Author, co-author :
Ambrosetti, A.;  Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin, Germany
Alfè, D.;  Department of Earth Sciences, London Centre for Nanotechnology, University College, London WC1E6BT, United Kingdom
Distasio, R. A.;  Department of Chemistry, Princeton University, Princeton, NJ 08544, United States
TKATCHENKO, Alexandre ;  Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin, Germany
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Title :
Hard numbers for large molecules: Toward exact energetics for supramolecular systems
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Journal of Physical Chemistry Letters
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American Chemical Society, Washington, United States - District of Columbia
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Peer Reviewed verified by ORBi
Funders :
CER - Conseil Européen de la Recherche [BE]
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