Affordable Ab Initio Path Integral for Thermodynamic Properties via Molecular Dynamics Simulations Using...

Area of Science:

• Computational chemistry
• Quantum mechanics
• Molecular dynamics

Background:

• Path integral molecular dynamics (PIMD) is crucial for simulating nuclear quantum effects.
• Direct ab initio PIMD simulations are computationally prohibitive for many systems.

Purpose of the Study:

• To develop a computationally efficient method for ab initio PIMD.
• To reduce the computational expense of simulating intramolecular proton transfer.

Main Methods:

• Implementation of reference-potential methods within PIMD.
• Simulation of proton transfer in protonated 1,8-bis(dimethylamino)naphthalene.
• Parallel postprocessing on computer clusters.

Main Results:

• A significant reduction in computational cost for ab initio PIMD simulations.
• Achieved nanosecond-timescale simulations with ab initio accuracy.
• Demonstrated a 545-fold reduction in CPU time compared to direct PIMD.

Conclusions:

• Reference-potential methods offer a viable strategy for efficient ab initio PIMD.
• Enables accurate thermodynamic property calculations for complex molecular systems.
• Facilitates the study of nuclear quantum effects at unprecedented scales.