title: Collective many-body van der Waals interactions in molecular systems.
abstract: Van der Waals (vdW) interactions are ubiquitous in molecules and condensed matter, and play a crucial role in determining the structure, stability, and function for a wide variety of systems. The accurate prediction of these interactions from first principles is a substantial challenge because they are inherently quantum mechanical phenomena that arise from correlations between many electrons within a given molecular system. We introduce an efficient method that accurately describes the nonadditive many-body vdW energy contributions arising from interactions that cannot be modeled by an effective pairwise approach, and demonstrate that such contributions can significantly exceed the energy of thermal fluctuations--a critical accuracy threshold highly coveted during molecular simulations--in the prediction of several relevant properties. Cases studied include the binding affinity of ellipticine, a DNA-intercalating anticancer agent, the relative energetics between the A- and B-conformations of DNA, and the thermodynamic stability among competing paracetamol molecular crystal polymorphs. Our findings suggest that inclusion of the many-body vdW energy is essential for achieving chemical accuracy and therefore must be accounted for in molecular simulations.
authors.affiliation: Department of Chemistry, Princeton University, Princeton, NJ 08544, USA.
authors.forename: Robert A
authors.initials: RA
authors.lastname: DiStasio
authors.forename: O Anatole
authors.initials: OA
authors.lastname: von Lilienfeld
authors.forename: Alexandre
authors.initials: A
authors.lastname: Tkatchenko
mesh_terms: D000082:Acetaminophen / Q000737:chemistry; D055598:Chemical Phenomena; D004247:DNA / Q000737:chemistry*; D004611:Ellipticines / Q000737:chemistry; D008958:Models, Molecular; D008968:Molecular Conformation; D056004:Molecular Dynamics Simulation; D011789:Quantum Theory; D013816:Thermodynamics
chemical_list: D004611:Ellipticines; C034192:ellipticine; D000082:Acetaminophen; D004247:DNA