Collective many-body van der Waals interactions in molecular systems

Proc Natl Acad Sci U S A. 2012 Sep 11;109(37):14791-5. doi: 10.1073/pnas.1208121109. Epub 2012 Aug 24.

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.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Acetaminophen / chemistry
  • Chemical Phenomena*
  • DNA / chemistry*
  • Ellipticines / chemistry
  • Models, Molecular*
  • Molecular Conformation*
  • Molecular Dynamics Simulation
  • Quantum Theory*
  • Thermodynamics

Substances

  • Ellipticines
  • ellipticine
  • Acetaminophen
  • DNA