Effective Force Field for Liquid Hydrogen Fluoride from Ab Initio Molecular Dynamics Simulation Using the Force-Matching Method

• Published in: The journal of physical chemistry. B 2005-04, Vol.109 (14), p.6573-6586
• Main Authors: Izvekov, Sergei, Voth, Gregory A.
• Format: Article
• Language: English
• Subjects: Chemistry, Physical - methods; Computer Simulation; Dimerization; Electrons; Hydrofluoric Acid - chemistry; Models, Chemical; Models, Statistical; Models, Theoretical; Molecular Conformation; Probability; Software; Temperature; Thermodynamics
• ISSN: 1520-6106; 1520-5207
• DOI: 10.1021/jp0456685

A recently developed force-matching method for obtaining effective force fields for condensed matter systems from ab initio molecular dynamics (MD) simulations has been applied to fit a simple nonpolarizable two-site pairwise force field for liquid hydrogen fluoride. The ab initio MD in this case was a Car−Parrinello (CP) MD simulation of 64 HF molecules at nearly ambient conditions within the Becke−Lee−Yang−Parr approximation to the electronic density functional theory. The force-matching procedure included a fit of short-ranged nonbonded forces, bonded forces, and atomic partial charges. The performance of the force-match potential was examined for the gas-phase dimer and for the liquid phase at various temperatures. The model was able to reproduce correctly the bent structure and energetics of the gas-phase dimer, while the results for the structural properties, self-diffusion, vibrational spectra, density, and thermodynamic properties of liquid HF were compared to both experiment and the CP MD simulation. The force-matching model performs well in reproducing nearly all of the liquid properties as well as the aggregation behavior at different temperatures. The model is computationally cheap and compares favorably to many more computationally expensive potential energy functions for liquid HF.