Theoretical and Computational Chemistry

Affordable Ab Initio Path Integral for Thermodynamic Properties via Molecular Dynamics Simulations Using Semiempirical Reference Potential

Authors

  • Yuanfei Xue State Key Laboratory of Precision Spectroscopy, School of Physics and Electronic Science, East China Normal University, Shanghai 200062, China ,
  • Jia-Ning Wang State Key Laboratory of Precision Spectroscopy, School of Physics and Electronic Science, East China Normal University, Shanghai 200062, China ,
  • Wenxin Hu The Computer Center, School of Data Science & Engineering, East China Normal University, Shanghai 200062, China ,
  • Jun Zheng The Computer Center, School of Data Science & Engineering, East China Normal University, Shanghai 200062, China ,
  • Yongle Li Department of Physics, International Center of Quantum and Molecular Structure, and Shanghai Key Laboratory of High Temperature Superconductors, Shanghai University, Shanghai 200444, China ,
  • Xiaoliang Pan Department of Chemistry and Biochemistry, University of Oklahoma, Norman, Oklahoma 73019, United States ,
  • Yan Mo State Key Laboratory of Precision Spectroscopy, School of Physics and Electronic Science, East China Normal University, Shanghai 200062, China ,
  • Yihan Shao Department of Chemistry and Biochemistry, University of Oklahoma, Norman, Oklahoma 73019, United States ,
  • Lu Wang Department of Chemistry and Chemical Biology, Institute for Quantitative Biomedicine, Rutgers University, Piscataway, New Jersey 08854, United States ,
  • Ye Mei State Key Laboratory of Precision Spectroscopy, School of Physics and Electronic Science, East China Normal University, Shanghai 200062, China

Abstract

Path integral molecular dynamics (PIMD) is becoming a routinely applied method for the incorporation of the nuclear quantum effect in computer simulations. However, direct PIMD simulations at an ab initio level of theory are formidably expensive. Using the protonated 1,8-bis(dimethylamino)naphthalene molecule as an example, we show in this work that the computational expense for the intra-molecular proton transfer between the two nitrogen atoms can be remarkably reduced by implementing the idea of reference-potential methods. The simulation time can be easily extended to a scale of nanosecond while maintaining the accuracy on an ab initio level of theory for thermodynamic properties. In addition, the post-processing can be carried out in parallel on massive computer nodes. A 545-fold reduction in the total CPU time can be achieved in this way as compared to a direct PIMD simulation at the same ab initio level of theory.

Content

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