Reference : Collective many-body van der Waals interactions in molecular systems
Scientific journals : Article
Physical, chemical, mathematical & earth Sciences : Multidisciplinary, general & others
Collective many-body van der Waals interactions in molecular systems
DiStasio Jr., R. A. [Department of Chemistry, Princeton University, Princeton, NJ 08544, United States]
Von Lilienfeld, O. A. [Argonne Leadership Computing Facility, Argonne National Laboratory, Argonne, IL 60439, United States]
Tkatchenko, Alexandre mailto [Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin, Germany]
Proceedings of the National Academy of Sciences of the United States of America
Yes (verified by ORBilu)
[en] Dispersion interactions ; DNA stability ; Force fields ; Intermolecular interactions ; Polymorphism ; DNA ; DNA conformation ; DNA structure ; Acetaminophen ; DNA ; Ellipticines ; Models, Molecular ; Molecular Conformation ; Molecular Dynamics Simulation ; Physicochemical Processes ; Quantum Theory ; Thermodynamics
[en] 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.

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