arXiv subjects

Zachary K. Goldsmith

Publications and source records attributed to Zachary K. Goldsmith.

2 recordsLinked to original sources

arXiv2026

Adsorption energies and decomposition barrier heights for ethylene carbonate on the surface of lithium from cluster-based quantum chemistry

For ethylene carbonate on the (100) surface of lithium, we calculate the adsorption energy in two binding motifs as well as the barrier height for a ring-opening decomposition reaction. We validate a scheme for producing results in the thermodynamic limit by correcting results obtained on finite lithium clusters containing only 40-100 atoms, which enables the use of hybrid density functionals, the random-phase approximation, and correlated wavefunction theories such as coupled-cluster theory and auxiliary-field quantum Monte Carlo. We find that the high-level theories agree to within 2-5 kcal/mol and can therefore serve as benchmarks for more affordable methods. Using our reference data, we demonstrate that generalized gradient approximation functionals, such as PBE, are not sufficiently accurate for reaction barrier heights, and we identify $ω$B97X-V as an especially promising functional for the interfacial chemistry of electrolyte solvents at lithium metal anodes.

cond-mat.mtrl-sci↗

arXiv2024

Electrical double layer and capacitance of TiO2 electrolyte interfaces from first principles simulations

The electrical double layer (EDL) at aqueous solution-metal oxide interfaces critically affects many fundamental processes in electrochemistry, geology and biology, yet understanding its microscopic structure is challenging for both theory and experiments. Here we employ ab initio-based machine learning potentials including long-range electrostatics in large-scale atomistic simulations of the EDL at the TiO2-electrolyte interface. Our simulations provide a molecular-scale picture of the EDL that demonstrates the limitations of standard mean-field models. We further develop a method to accurately calculate the electrostatic potential drop at the interface. The computed capacitance originating from the adsorbed charges and the potential drop agrees with experiments, supporting the reliability of our description of the EDL. The larger interfacial capacitance of basic relative to acidic solutions originates from the higher affinity of the cations for the oxide surface and gives rise to distinct charging mechanisms on negative and positive surfaces.

physics.chem-ph↗