Effects of paramagnetic fluctuations on the thermochemistry of MnO(100) surfaces in the oxygen evolution reaction

We investigated the effects of paramagnetic (PM) fluctuations on the thermochemistry of the MnO(100) surface in the oxygen evolution reaction (OER) using the "noncollinear magnetic sampling method plus U " (NCMSM+ U ). Various physical properties, such as the electronic structure, free ene...

Full description

Saved in:
Bibliographic Details
Published in:Physical chemistry chemical physics : PCCP 2021-01, Vol.23 (2), p.859-865
Main Authors: Yoon, Sangmoon, Jin, Kyoungsuk, Lee, Sangmin, Nam, Ki Tae, Kim, Miyoung, Kwon, Young-Kyun
Format: Article
Language:English
Subjects:
Antiferromagnetism
Charge transfer
Chemical bonds
Chemical reactions
Electronic structure
Free energy
Magnetic properties
Manganese oxides
Oxygen evolution reactions
Physical properties
Thermochemistry
Valence band
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:We investigated the effects of paramagnetic (PM) fluctuations on the thermochemistry of the MnO(100) surface in the oxygen evolution reaction (OER) using the "noncollinear magnetic sampling method plus U " (NCMSM+ U ). Various physical properties, such as the electronic structure, free energy, and charge occupation, of the MnO(100) surface in the PM state with several OER intermediates, were reckoned and compared to those in the antiferromagnetic (AFM) state. We found that PM fluctuation enhances charge transfer from a surface Mn ion to each of the intermediates and strengthens the chemical bond between them, while not altering the overall features, such as the rate determining step and resting state, in reaction pathways. The enhanced charge transfer can be attributed to the delocalized nature of valence bands observed in the PM surface. In addition, it was observed that chemical-bond enhancement depends on the intermediates, resulting in significant deviations in reaction energy barriers. Our study suggests that PM fluctuations play a significant role in the thermochemistry of chemical reactions occurring on correlated oxide surfaces. We investigated the effects of paramagnetic (PM) fluctuations on the thermochemistry of the MnO(100) surface in the oxygen evolution reaction (OER) using the "noncollinear magnetic sampling method plus U " (NCMSM+ U ).
ISSN:1463-9076
1463-9084
DOI:10.1039/d0cp03779f