A Polarizable QM/MM Explicit Solvent Model for Computational Electrochemistry in Water

Citations Over TimeTop 10% of 2012 papers

Abstract

We present a quantum mechanical/molecular mechanical (QM/MM) explicit solvent model for the computation of standard reduction potentials E0. The QM/MM model uses density functional theory (DFT) to model the solute and a polarizable molecular mechanics (MM) force field to describe the solvent. The linear response approximation is applied to estimate E0 from the thermally averaged electron attachment/detachment energies computed in the oxidized and reduced states. Using the QM/MM model, we calculated one-electron E0 values for several aqueous transition-metal complexes and found substantially improved agreement with experiment compared to values obtained from implicit solvent models. A detailed breakdown of the physical effects in the QM/MM model indicates that hydrogen-bonding effects are mainly responsible for the differences in computed values of E0 between the QM/MM and implicit models. Our results highlight the importance of including solute-solvent hydrogen-bonding effects in the theoretical modeling of redox processes.

Related Papers

• → A Polarizable QM/MM Explicit Solvent Model for Computational Electrochemistry in Water(2012)82 cited
• → Solvent Effects on Electronically Excited States: QM/Continuum Versus QM/Explicit Models(2018)32 cited
• → Towards a transferable nonelectrostatic model for continuum solvation: The electrostatic and nonelectrostatic energy correction model(2022)3 cited
• → Vibrational analysis beyond the harmonicity from Ab initio molecular dynamics: Case of cytosine in its anhydrous and aqueous forms(2012)16 cited
• → Using theoretical descriptors to model solvent effects in the isomerization ofcis-stilbene(1996)5 cited