Get access

A partition function-based weighting scheme in force field parameter development using ab initio calculation results in global configurational space

Authors

  • Yao Wu,

    1. Graduate Program in Peking Union Medical College and Chinese Academy of Medical Sciences, Beijing 100730, China
    2. National Institute of Biological Sciences, Zhongguancun Life Science Park, Beijing 102206, China
    Search for more papers by this author
  • Xiaodong Dai,

    1. Beijing Institute of Pharmaceutical Chemistry, Beijing 102205, China
    Search for more papers by this author
  • Niu Huang,

    Corresponding author
    1. Graduate Program in Peking Union Medical College and Chinese Academy of Medical Sciences, Beijing 100730, China
    2. National Institute of Biological Sciences, Zhongguancun Life Science Park, Beijing 102206, China
    • National Institute of Biological Sciences, Zhongguancun Life Science Park, Beijing 102206, China
    Search for more papers by this author
  • Lifeng Zhao

    Corresponding author
    1. National Institute of Biological Sciences, Zhongguancun Life Science Park, Beijing 102206, China
    • National Institute of Biological Sciences, Zhongguancun Life Science Park, Beijing 102206, China
    Search for more papers by this author

Abstract

In force field parameter development using ab initio potential energy surfaces (PES) as target data, an important but often neglected matter is the lack of a weighting scheme with optimal discrimination power to fit the target data. Here, we developed a novel partition function-based weighting scheme, which not only fits the target potential energies exponentially like the general Boltzmann weighting method, but also reduces the effect of fitting errors leading to overfitting. The van der Waals (vdW) parameters of benzene and propane were reparameterized by using the new weighting scheme to fit the high-level ab initio PESs probed by a water molecule in global configurational space. The molecular simulation results indicate that the newly derived parameters are capable of reproducing experimental properties in a broader range of temperatures, which supports the partition function-based weighting scheme. Our simulation results also suggest that structural properties are more sensitive to vdW parameters than partial atomic charge parameters in these systems although the electrostatic interactions are still important in energetic properties. As no prerequisite conditions are required, the partition function-based weighting method may be applied in developing any types of force field parameters. © 2013 Wiley Periodicals, Inc.

Get access to the full text of this article

Ancillary