Ab initio potential energy surfaces calculation via restricted Hartree–Fock for molecular dynamics simulation: a comprehensive review

This study systematically analyzes the restricted Hartree–Fock (RHF) method, which is used to calculate the potential energy surface (PES) of closed-shell molecular systems. In this process, an optimized algorithm for the calculation of the RHF matrix based on the Roothaan equation is designed and a detailed programming strategy for its implementation is presented. The algorithm is highly stable in the Psi4 library and Python environment and demonstrates the ability to efficiently calculate PES for basic organic compounds such as ethane (C2H6), propane (C3H8), and butane (C4H10). Furthermore, the PES derived by the proposed algorithm plays a crucial role in determining the force field parameters for CHARMM, AMBER, COMPASS, and DREIDING, which are essential for molecular dynamics simulations. The findings of this study provide fundamental insights into the study of first-principle-based molecular dynamics simulations, which are expected to expand the scope of applications in basic research for an ab initio computational chemistry and physics.