Hybrid Functional and Plane Waves based Ab Initio Molecular Dynamics Study of the Aqueous Fe$^{2+}$/Fe$^{3+}$ Redox Reaction

TL;DR

This paper demonstrates a method to perform hybrid functional ab initio molecular dynamics simulations efficiently to study the aqueous Fe$^{2+}$/Fe$^{3+}$ redox reaction, improving accuracy over GGA functionals.

Contribution

It applies the noise-stabilized MD approach with localized orbitals to enable long hybrid functional AIMD trajectories for complex redox systems.

Findings

Hybrid functional AIMD trajectories successfully obtained.

Redox properties match experimental data.

Method reduces computational cost significantly.

Abstract

Kohn-Sham density functional theory and plane wave basis set based ab initio molecular dynamics (AIMD) simulation is a powerful tool for studying complex reactions in solutions, such as electron transfer (ET) reactions involving Fe$^{2+}$/Fe$^{3+}$ ions in water. In most cases, such simulations are performed using density functionals at the level of Generalized Gradient Approximation (GGA). The challenge in modelling ET reactions is the poor quality of GGA functionals in predicting properties of such open-shell systems due to the inevitable self-interaction error (SIE). While hybrid functionals can minimize SIE, AIMD at that level of theory is typically 150 times slower than GGA for systems containing ~100 atoms. Among several approaches reported to speed-up AIMD simulations with hybrid functionals, the noise-stabilized MD (NSMD) procedure, together with the use of localized orbitals to compute the required exchange integrals, is an attractive option. In this work, we demonstrate the application of the NSMD approach for studying the Fe$^{2+}$/Fe$^{3+}$ redox reaction in water. It is shown here that long AIMD trajectories at the level of hybrid density functionals can be obtained using this approach. Redox properties of the aqueous Fe$^{2+}$/Fe$^{3+}$ system computed from these simulations are compared with the available experimental data for validation.