Lithium-oxygen charge transfer interaction: a deformation density analysis study

Document Type : Research Paper


Chemistry Department, College of Sciences, Yasouj University, Yasouj, Iran


Lithium and oxygen interaction plays a cornerstone role in lithium ion and lithium air batteries and lithium based technologies. In this way, oxidation and reduction of neutral and charged lithium is the key process in its application as power source and sustainable energies. Since both oxidation and reduction are based on charge transfer in molecular scale, they can be analyzed via electronic structure changes. Two types of fragmentations for charged complexes were suggested, in which the positive charge was located on either lithium or oxygen fragment. Deformation density analysis is a recently developed technique for identification of different intermolecular interactions in the context of quantum chemical language. In this analysis, the molecular orbitals of isolated fragments were employed to build non-interacting and anti-symmetrized fragments and the corresponding density matrices to find deformation density matrix of each one. In the present study, two types of deformation density including kinetic energy pressure and relaxation analyses were accomplished for lithium and oxygen interaction at B3LYP/6-311+G* theoretical level. Electronic deformation orbitals responsible for charge transfer were identified with respect to their eigenvalues. The results showed how these two competed with each other in neutral and charged complexes with different fragmentations.


Main Subjects

[1] Kwak WJ, Rosy, Sharon D, Xia C, Kim H, Johnson LR, et al. Lithium–oxygen batteries and related systems: potential, status, and future. Chemical Reviews. 2020;120(14):6626–6683.
[2] Ding S, Yu X, Ma ZF, Yuan X. A review of rechargeable aprotic lithium–oxygen batteries based on theoretical and computational investigations. Journal of Materials Chemistry A. 2021;9(13):8160–8194.
[3] Zhang X, Dong P, Song MK. Advances in Lithium–Oxygen Batteries Based on Lithium Hydroxide Formation and Decomposition. Frontiers in Chemistry. 2022;10:923936.
[4] Ezeigwe ER, Dong L, Manjunatha R, Zuo Y, Deng SQ, Tan M, et al. A review of lithiumO2/CO2 and lithium-CO2 batteries: Advanced electrodes/materials/electrolytes and functional mechanisms. Nano Energy. 2022;95:106964.
[5] Dang C, Mu Q, Xie X, Sun X, Yang X, Zhang Y, et al. Recent progress in cathode catalyst for nonaqueous lithium oxygen batteries: a review. Advanced Composites and Hybrid Materials. 2022;5(2):606–626.
[6] Dou Y, Xie Z, Wei Y, Peng Z, Zhou Z. Redox mediators for high-performance lithium– oxygen batteries. National Science Review. 2022;9(4):nwac040.
[7] Suryatna A, Raya I, Thangavelu L, Alhachami FR, Kadhim MM, Altimari US, et al. A review of highenergy density  lithium-air battery technology: investigating the effect of oxides and nanocatalysts. Journal of Chemistry. 2022;2022:1–32.
[8] Du D, Zhu Z, Chan KY, Li F, Chen J. Photoelectrochemistry of oxygen in rechargeable Li–O2 batteries. Chemical Society Reviews. 2022;51(6):1846–1860.
[9] Lu J, Li L, Park JB, Sun YK, Wu F, Amine K. Aprotic and aqueous Li–O2 batteries. Chemical reviews. 2014;114(11):5611–5640.
[10] McCloskey BD, Bethune DS, Shelby RM, Girishkumar G, Luntz AC. Solvents’ critical role in nonaqueous lithium–oxygen battery electrochemistry. The Journal of Physical Chemistry Letters. 2011;2(10):1161–1166.
[11] Xu W, Wang J, Ding F, Chen X, Nasybulin E, Zhang Y, et al. Lithium metal anodes for rechargeable batteries. Energy & Environmental Science. 2014;7(2):513–537.
[12] Zhang T, Zhou H. Lithium-oxygen batteries: from electrochemistry to materials science. Angewandte
Chemie International Edition. 2017;56:8364–8383.
[13] Ravaei I, Azami SM. Block deformation analysis: Density matrix blocks as intramolecular deformation density. Journal of Computational Chemistry. 2020;41(29):2446–2458.
[14] De Lange JH, Cukrowski I. Toward deformation densities for intramolecular interactions without radical reference states using the fragment, atom, localized, delocalized, and interatomic (FALDI) charge density decomposition scheme. Journal of Computational Chemistry. 2017;38(13):981–997.
[15] Shahamirian M, Azami S. Encapsulation of glycine inside C60 fullerene: Impact of confinement. Physics Letters A. 2019;383(36):126004.
[16] Fakhraee S, Azami S. Orbital representation of kinetic energy pressure. The Journal of chemical physics. 2009;130(8).
[17] Ghanavati F, Azami S. Topological analysis of steric and relaxation deformation densities. Molecular Physics. 2017;115(6):743–756.
[18] Amini S, Azami SM. Asymmetric deformation density analysis in carbon nanotubes. International Journal of Quantum Chemistry. 2020;120(17):e26277.
[19] Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, et al.. Gaussian˜16 Revision B.01; 2016. Gaussian Inc. Wallingford CT.
[20] Azami SM. Densitizer Ver. 2.0.0;.
[21] Dennington R, Keith T, Millam J. GaussView, Version 6.1; 2016. Semichem Inc., Shawnee Mission, KS.
[22] Yang W, Kim DY, Yang L, Li N, Tang L, Amine K, et al. Oxygen-Rich Lithium Oxide Phases Formed at High Pressure for Potential Lithium–Air Battery Electrode. Advanced Science. 2017;4(9):1600453.
[23] Lau KC, Curtiss LA, Greeley J. Density functional investigation of the thermodynamic stability of lithium oxide bulk crystalline structures as a function of oxygen pressure. The Journal of Physical Chemistry C. 2011;115(47):23625–23633.
[24] Hong M, Byon HR. Singlet oxygen in lithiumoxygen batteries. Batteries & Supercaps. 2021;4(2):286–293.
[25] Soltay LG, Henderson GS. The structure of lithium-containing silicate and germanate glasses. The Canadian Mineralogist. 2005;43(5):1643–1651.
[26] Liu W, Su Q, Yu L, Du G, Li C, Zhang M, et al. Understanding reaction mechanism of oxygen evolution reaction using Ru single atoms as catalyst for Li-O2 battery. Journal of Alloys and Compounds. 2021;886:161189.
[27] Liu Y, P´erez-Luna VH, Prakash J. Quantitative elucidation of cathode reaction mechanisms in LiO2 batteries within high donor number solvents. Electrochimica Acta. 2024;475:143669.
[28] Xia C, Kwok CY, Nazar LF. A high-energydensity lithium-oxygen battery based on a reversible four-electron conversion to lithium oxide. Science. 2018;361(6404):777–781. Available from: