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

Path integral molecular dynamics (PIMD) is becoming a routinely applied method for incorporating 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 intramolecular 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 nanoseconds while maintaining the accuracy on an ab initio level of theory for thermodynamic properties. In addition, postprocessing 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.

Automated summary

The use of reference-potential methods can significantly reduce the computational cost of path integral molecular dynamics simulations, allowing for simulation time to be extended to the scale of nanoseconds while maintaining accuracy. Additionally, postprocessing can be carried out in parallel on massive computer nodes, leading to a 545-fold reduction in total CPU time compared to direct PIMD simulations at the same ab initio level of theory.