Logo
ScienceStack
Table of Contents
Fetching ...
Sign In

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

Ethan A. Vo, Hung T. Vuong, Zachary K. Goldsmith, Hong-Zhou Ye, Yujing Wei, Sohang Kundu, Ardavan Farahvash, Garvit Agarwal, Richard A. Friesner, Timothy C. Berkelbach

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

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

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 B97X-V as an especially promising functional for the interfacial chemistry of electrolyte solvents at lithium metal anodes.
Paper Structure (4 sections, 3 equations, 4 figures, 3 tables)

This paper contains 4 sections, 3 equations, 4 figures, 3 tables.

Table of Contents

  1. Introduction
  2. Methods
  3. Results
  4. Conclusion

Figures (4)

  • Figure 1: Geometries of ethylene carbonate on lithium for the top adsorbed structure (a), the parallel adsorbed structure (b), and the transition state to ring opening from the parallel structure (c).
  • Figure 2: Adsorption energy in the top (a) and parallel (b) geometries, and decomposition reaction barrier height (c) for EC on hemispherical clusters of increasing size. Results are shown for the methods and basis sets indicated in the legend, and faint lines indicate approximate extensions of the data based on the PBE/def2-SVP results. Geometries at top show the parallel adsorption geometry with clusters containing 50, 100, and 300 lithium atoms.
  • Figure 3: The same as in Fig. \ref{['fig:pbe_ccsd']}, but for correlated methods indicated in the legend. AFQMC results are shown with statistical error bars.
  • Figure 4: The same is in Figs. \ref{['fig:pbe_ccsd']} and \ref{['fig:corr']}, but for the various density functionals indicated.