Pathways for Electron Transfer at MgO–Water Interfaces from Ab Initio Molecular Dynamics

Ding, Zhutian; Goldsmith, Zachary K.; Selloni, Annabella

doi:10.1021/jacs.1c13250

Title: Pathways for Electron Transfer at MgO–Water Interfaces from Ab Initio Molecular Dynamics

Journal Article · 21 January 2022 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.1c13250 · OSTI ID:1994961

Ding, Zhutian ^[1]; Goldsmith, Zachary K. ^[2];

^[2]

Princeton Univ., NJ (United States); Princeton University, Department of Chemistry
Princeton Univ., NJ (United States)

The nature of electron transfer across metal oxide–water interfaces depends significantly on the band gap of the oxide and its band edge energies relative to the potentials of relevant aqueous redox couples. Here we focus on the water interface with MgO, a prototypical wide band gap oxide whose conduction band edge is close in energy to that of water. We investigate the behavior of an excess electron at and out of equilibrium near the interface using ab initio molecular dynamics based on hybrid density functional theory. Our simulations show that under equilibrium conditions the excess electron (donated by an Al impurity in MgO) localizes to a midgap defect state comparable in energy and shape to a hydrated electron in bulk water. To characterize the electron transfer from the conduction band of MgO to interfacial product states, we dope near-equilibrium configurations of the pristine MgO–water system with Al and run short trajectories of these instantaneously out-of-equilibrium systems. Here we observe two distinct products associated with the excess electron: a surface-localized electron (e_surf–) and an aqueous hydrogen radical (H^•). The H^• pathway exhibits a much higher activation barrier despite being more exoergic, making e_surf– the kinetic product. Our characterization of the pathways on the basis of Marcus theory is consistent with the poor observed utility of MgO for water radiolysis. Moreover, we anticipate that the computational framework employed here will be broadly applicable to assessing electron transfer mechanisms at aqueous, photocatalytic interfaces.

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Research Organization:: Princeton Univ., NJ (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: SC0019394; SC0007347; AC02-05CH11231

OSTI ID:: 1994961

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 4 Vol. 144; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Magnesium oxide
charge transfer
computational chemistry
free energy
interfaces

Title: Pathways for Electron Transfer at MgO–Water Interfaces from Ab Initio Molecular Dynamics

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