Calculation of solvation free energies of Li+ and O2- ions and neutral lithium-oxygen compounds in acetonitrile using mixed cluster/continuum models

Vyacheslav S. Bryantsev

doi:10.1007/s00214-012-1250-7

Calculation of solvation free energies of Li⁺ and O₂^- ions and neutral lithium-oxygen compounds in acetonitrile using mixed cluster/continuum models

Vyacheslav S. Bryantsev

Research output: Contribution to journal › Article › peer-review

41 Scopus citations

Abstract

Solvation effects play a major role in determining the cycling characteristics of the non-aqueous rechargeable Li-air battery. We use a mixed cluster/continuum solvent model with varying number of explicit solvent molecules (n = 4-10) to calculate the solvation free energies (ΔG_solv^*) of Li⁺ and O₂^- ions and neutral LiO₂, Li₂O₂, LiO, and Li₂O species in acetonitrile solvent. Calculations for complexes with the full first solvation shell around Li⁺ (n = 4) and O₂^- (n = 8) show excellent agreement with the solvation free energies obtained using the cluster pair approximation (the error is below 2.0 kcal/ mol). The use of the pure continuum model fitted to reproduce the experimental values of ΔG_solv^*(Li⁺) and ΔG_solv^*(O₂^-) gives the solvation free energies of various lithium-oxygen species (LixOy; x, y = 1, 2) that are in excellent agreement with the results obtained using mixed cluster/continuum models (n ≥ 8). This provides a theoretical framework for including solvent effects in the theoretical models of oxygen reduction and evolution reactions in the aprotic Li-air battery.

Original language	English
Article number	1250
Pages (from-to)	1-11
Number of pages	11
Journal	Theoretical Chemistry Accounts
Volume	131
Issue number	7
DOIs	https://doi.org/10.1007/s00214-012-1250-7
State	Published - Jul 2012
Externally published	Yes

Funding

I am indebted to Dr. Mario Blanco for providing me with the algorithm for sampling the initial configurations of solvated clusters. This work was supported by Liox Power, Inc., Pasadena, CA.

Funders	Funder number
Liox Power, Inc.

Keywords

Acetonitrile solvent
Continuum and mixed cluster/continuum solvent models
Lithium ion
Lithium-oxygen compounds
Solvation free energy
Superoxide ion

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.1007/s00214-012-1250-7

Cite this

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title = "Calculation of solvation free energies of Li+ and O2- ions and neutral lithium-oxygen compounds in acetonitrile using mixed cluster/continuum models",

abstract = "Solvation effects play a major role in determining the cycling characteristics of the non-aqueous rechargeable Li-air battery. We use a mixed cluster/continuum solvent model with varying number of explicit solvent molecules (n = 4-10) to calculate the solvation free energies (ΔGsolv*) of Li+ and O2- ions and neutral LiO2, Li2O2, LiO, and Li2O species in acetonitrile solvent. Calculations for complexes with the full first solvation shell around Li+ (n = 4) and O2- (n = 8) show excellent agreement with the solvation free energies obtained using the cluster pair approximation (the error is below 2.0 kcal/ mol). The use of the pure continuum model fitted to reproduce the experimental values of ΔGsolv*(Li+) and ΔGsolv*(O2-) gives the solvation free energies of various lithium-oxygen species (LixOy; x, y = 1, 2) that are in excellent agreement with the results obtained using mixed cluster/continuum models (n ≥ 8). This provides a theoretical framework for including solvent effects in the theoretical models of oxygen reduction and evolution reactions in the aprotic Li-air battery.",

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