Dispersion interactions; DNA stability; Force fields; Intermolecular interactions; Polymorphism; DNA; DNA conformation; DNA structure; Acetaminophen; Ellipticines; Models, Molecular; Molecular Conformation; Molecular Dynamics Simulation; Physicochemical Processes; Quantum Theory; Thermodynamics
Abstract :
[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.
Disciplines :
Physical, chemical, mathematical & earth Sciences: Multidisciplinary, general & others
Identifiers :
eid=2-s2.0-84866265918
Author, co-author :
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