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

TL;DR

This study calculates adsorption energies and decomposition barriers for ethylene carbonate on lithium surfaces, validating a cluster-based scheme to enable high-level quantum chemistry methods and identifying accurate functionals for interfacial chemistry.

Contribution

The paper introduces a validated scheme for applying high-level quantum chemistry to lithium surfaces using finite clusters, providing benchmark data for reaction barriers and adsorption energies.

Findings

High-level theories agree within 2-5 kcal/mol, serving as benchmarks.

GGA functionals like PBE are insufficient for accurate barrier heights.

$97X-V$ functional shows promise for interfacial chemistry modeling.

Abstract

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 $\omega$B97X-V as an especially promising functional for the interfacial chemistry of electrolyte solvents at lithium metal anodes.