Eric Borguet | Searcharxiv

arXiv2024

Determining the Dielectric Constant of Solid/Liquid Interfaces

The dielectric constant ($\varepsilon^{\prime}$) of interfacial water is an important parameter, but its measurement has posed challenges, and no consensus has been reached on a generalized expression. We derived a formula for $\varepsilon^{\prime}$ of a buried interface using the slab model for a half-solvated sphere: $ \varepsilon^{\prime}=\varepsilon_1 \varepsilon_2\left(\varepsilon_2-\varepsilon_1+6\right) / 2\left(2 \varepsilon_2+\varepsilon_1\right)$, where $\varepsilon_1$ and $\varepsilon_2$ are the dielectric constants of the solid and liquid phases, respectively. We experimentally validated this expression using vibrational sum frequency generation and Fresnel factor calculations for interfaces of alumina with water ($ \mathrm{H_2O} $ and $ \mathrm{D_2O} $) and acetonitrile. This fills an important knowledge gap in the description of the dielectric constant of interfaces.

physics.chem-ph↗

arXiv2024

Comparing Meta-GGAs, +U Corrections, and Hybrid Functionals for Polaronic Point Defects in Layered MnO$_2$, NiO$_2$, and KCoO$_2$

Defects in a material can significantly tune properties and enhance utility. Hybrid functionals like HSE06 are often used to describe solids with such defects. However, geometry optimization (including accounting for effects such as Jahn-Teller distortion) using hybrid functionals is challenging for the large supercells needed for defect study. The proposed r$^2$SCAN+rVV10+U+$\mathrm{U_d}$ method, which is computationally much cheaper and faster than hybrid functionals, can successfully describe defects in materials with the proper choice of U (for the d orbitals of the host atom) and $\mathrm{U_d}$ (for those of the defect atom), as shown here for small polaron defects in layered transition-metal oxides. For a range of U and $\mathrm{U_d}$ around literature values (from solid-state reaction energies) for a given transition-metal ion and its oxidation state, we find that this approach predicts localized polaronic states in band gaps, as hybrid functionals do. The layered materials birnessite ($\mathrm{K_nMnO_2}, n=0.03 $) and $\mathrm{K_nNiO_2},n=0.03$, with one K atom intercalated between layers in a supercell, are found to have one localized occupied $\mathrm{e_g}$ polaronic state on the transition metal ion reduced by the insertion of the K atom, when the geometry is calculated as above using published U values. The expected Jahn-Teller distortion is not observed when U=$\mathrm{U_d}$=0. Layered cobalt oxide with additional potassium ions intercalated ($\mathrm{K_nCoO_2},n=1.03$) is different, due to a dramatic difference in electronic configuration of the defected Co(II) ion: A single extra K atom in the supercell leads to four localized electrons in the band gap, using standard U values, and even for U=$\mathrm{U_d}$=0.

physics.comp-ph↗