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Quenching of magnetism in NaO2 due to electrostatic interaction induced partial orbital ordering

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Abstract

The transport properties of sodium superoxide (NaO2) are governed by the transfer of charge between O2− complexes. Although it goes through a plethora of structural phase transitions, its electronic and magnetic ground state remains shrouded in mystery. In this work, we perform first-principles density functional theory (DFT) calculations to understand the relationship between electronic structure and the reason for the non-observation of an antiferromagnetic (AFM) ground state in NaO2 vis-a-vis in KO2. In the cubic phase, uniform < Na–O-Na bond angles result in high symmetry and hence degeneracy in the O-2p orbitals. The freely rotating O2− molecules result in orbital degeneracy and hence paramagnetism at room temperature. Although the degeneracy between the bonding and anti-bonding orbitals of O2 dimers is lifted in the pyrite phase, the degeneracy between σ (σ*) and π (π*) states is still maintained and hence orbital degeneracy is partially lifted as the dimers are restricted to four directions now. The O-π* states are localized in such a manner that results in a substantial magnetic moment in the π*-orbital. The < O–Na–O bond angle (= 180°) in the c-axis facilitates a superexchange mechanism and thereby the system should be AFM in the pyrite phase. In the marcasite phase, the O-atoms are aligned parallel in alternative planes. The preservation of degeneracy among the two π* orbitals leading to only long-range orbital ordering negates any chance of quasi-one-dimensional AFM spin chains in NaO2. The difference in magnetic ground states of NaO2 and KO2 arises due to the difference in the electrostatic repulsion between electrons of Na+ and K+ ions with the O2− dimers.

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Acknowledgements

The authors thank the West Bengal State University, Kolkata-700126, India, and Department of Higher Education, W.B, India, for financial and infrastructure support to carry out this work. The authors also render thanks to Debabrata Samata and Subhajit Chaudhury, M.Sc. students in the Dept. of Physics, West Bengal State University for their assistance to carry out this work.

Funding

This research was supported by the West Bengal State University, Kolkata-700126, India, and the Department of Higher Education, Government of West Bengal, India.

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Authors and Affiliations

  1. Department of Physics, Barasat Government College, Kolkata-700124, West Bengal, India

    Sarajit Biswas

  2. Department of Physics, West Bengal State University, Kolkata-700126, West Bengal, India

    Sarajit Biswas & Molly De Raychaudhury

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  1. Sarajit Biswas
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  2. Molly De Raychaudhury
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Contributions

S. B.: Framed the works, calculations, simulations, investigations, conceptualization and writing-original draft. M.D.R.: Framed the works, calculations, simulations, investigations, project administration, supervision, technical support, writing-original draft.

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Correspondence to Molly De Raychaudhury.

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Biswas, S., De Raychaudhury, M. Quenching of magnetism in NaO2 due to electrostatic interaction induced partial orbital ordering. J Mol Model 28, 13 (2022). https://doi.org/10.1007/s00894-021-05008-4

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