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

Authors :
Ambrosetti A
Alfè D
DiStasio RA Jr
Tkatchenko A
Source :
The journal of physical chemistry letters [J Phys Chem Lett] 2014 Mar 06; Vol. 5 (5), pp. 849-55. Date of Electronic Publication: 2014 Feb 17.
Publication Year :
2014

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.

Details

Language :
English
ISSN :
1948-7185
Volume :
5
Issue :
5
Database :
MEDLINE
Journal :
The journal of physical chemistry letters
Publication Type :
Academic Journal
Accession number :
26274077
Full Text :
https://doi.org/10.1021/jz402663k