Publication

Microscopic Picture of the Solvent Reorganization During Electron Transfer to Flavin in Water

Murat Kiliç
2019
Journal Articles

Abstract

The redox potential of molecular species is largely modulated by its molecular environment so that a change of the environment will lead to a different redox potential. However, a detailed molecular picture of reorganization of the environment upon reduction is still unclear. To unravel the details of the solvent reorganization during electron transfer, we have performed density functional theory-based molecular dynamics (DFT-MD) and hybrid quantum mechanics/molecular mechanics (QM/MM) simulations of the reduction of lumiflavin. Previously, we have calculated the reduction free energy curves of the redox half reactions of lumiflavin in water as a function of the instantaneous gap energy (Delta E) (J. Chem. Theory Comput. 2013, 9, 3889-3899). In this work, we focus on finding the changes in the solvent environment that correlate with this Delta E reaction coordinate. Comparing the QM/MM simulations, in which the solvent is modeled with an empirical force field, with the (full) DFT-MD simulations, we find that the response through electronic polarization plays a significant role in the latter case. Also a small charge transfer between flavin and solvent is observed in the full DFT treatment. As a result, we find only in the case of the QM/MM model a strong correlation between Delta E and the (pairwise computed) electrostatic potential (ESP) at the flavin due to the solvent. By analyzing the contribution of the ESP at the flavin per solvent molecule, we cannot only distinguish between the different modes of hydration by solvent molecules that coordinate at the hydrophilic and hydrophobic sides of the flavin molecule but also quantify their contribution to the reorganization free energy by measuring the ESP fluctuations per solvent molecule.

Official source

https://infoscience.epfl.ch/entities/publication/81e88385-4a89-46a8-9545-3fb8c3c9a325

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Murat Kiliç
2019
Journal Articles

Abstract

Official source

https://infoscience.epfl.ch/entities/publication/81e88385-4a89-46a8-9545-3fb8c3c9a325

About this result

Related concepts (32)

Computational chemistry

Computational chemistry is a branch of chemistry that uses computer simulation to assist in solving chemical problems. It uses methods of theoretical chemistry, incorporated into computer programs, to calculate the structures and properties of molecules, groups of molecules, and solids. It is essential because, apart from relatively recent results concerning the hydrogen molecular ion (dihydrogen cation, see references therein for more details), the quantum many-body problem cannot be solved analytically, much less in closed form.

Molecular dynamics

Molecular dynamics (MD) is a computer simulation method for analyzing the physical movements of atoms and molecules. The atoms and molecules are allowed to interact for a fixed period of time, giving a view of the dynamic "evolution" of the system. In the most common version, the trajectories of atoms and molecules are determined by numerically solving Newton's equations of motion for a system of interacting particles, where forces between the particles and their potential energies are often calculated using interatomic potentials or molecular mechanical force fields.

Reduction potential

Redox potential (also known as oxidation / reduction potential, ORP, pe, , or ) is a measure of the tendency of a chemical species to acquire electrons from or lose electrons to an electrode and thereby be reduced or oxidised respectively. Redox potential is expressed in volts (V). Each species has its own intrinsic redox potential; for example, the more positive the reduction potential (reduction potential is more often used due to general formalism in electrochemistry), the greater the species' affinity for electrons and tendency to be reduced.

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