Binding and diffusion of lithium in graphite: Quantum Monte Carlo benchmarks and validation of van der Waals density functional methods

P. Ganesh, Jeongnim Kim, Changwon Park, Mina Yoon, Fernando A. Reboredo, Paul R.C. Kent

Research output: Contribution to journalArticlepeer-review

124 Scopus citations

Abstract

Highly accurate diffusion quantum Monte Carlo (QMC) studies of the adsorption and diffusion of atomic lithium in AA-stacked graphite are compared with van der Waals-including density functional theory (DFT) calculations. Predicted QMC lattice constants for pure AA graphite agree with experiment. Pure AA-stacked graphite is shown to challenge many van der Waals methods even when they are accurate for conventional AB graphite. Highest overall DFT accuracy, considering pure AA-stacked graphite as well as lithium binding and diffusion, is obtained by the self-consistent van der Waals functional vdW-DF2, although errors in binding energies remain. Empirical approaches based on point charges such as DFT-D are inaccurate unless the local charge transfer is assessed. The results demonstrate that the lithium-carbon system requires a simultaneous highly accurate description of both charge transfer and van der Waals interactions, favoring self-consistent approaches.

Original languageEnglish
Pages (from-to)5318-5323
Number of pages6
JournalJournal of Chemical Theory and Computation
Volume10
Issue number12
DOIs
StatePublished - Dec 9 2014

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