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Hydrogenation of 3 d ‐metal oxide clusters: Effects on the structure and magnetic properties
Author(s) -
Gutsev G. L.,
Bozhenko K. V.,
Gutsev L. G.,
Utenyshev A. N.,
Aldoshin S. M.
Publication year - 2019
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.25739
Subject(s) - magnetic moment , antiferromagnetism , chemistry , ferrimagnetism , atom (system on chip) , polarizability , superexchange , metal , density functional theory , spin (aerodynamics) , condensed matter physics , singlet state , atomic physics , physics , computational chemistry , magnetization , molecule , excited state , magnetic field , organic chemistry , quantum mechanics , computer science , thermodynamics , embedded system
The geometrical structures and properties of the M 8 O 12 , M 8 O 12 H 8 , and M 8 O 12 H 12 clusters are explored using density functional theory with the generalized gradient approximation for all 3 d ‐metals M from Sc to Zn. It is found that the geometries and total spin magnetic moments of the clusters depended strongly on the 3 d ‐atom type and the hydrogenation extent. More than the half of all of the 30 clusters had singlet lowest total energy states, which could be described as either nonmagnetic or antiferromagnetic. Hydrogenation increases the total spin magnetic moments of the M 8 O 12 H 12 clusters when M MnNi, which become larger by four Bohr magneton than those of the corresponding unary clusters M 8 . Hydrogenation substantially affects such properties as polarizability, forbidden band gaps, and dipole moments. Collective superexchange where the local total spin magnetic moments of two atom squads are coupled antiparallel was observed in antiferromagnetic singlet states of Fe 8 O 12 H 8 and Co 8 O 12 H 8 , whereas the lowest total energy states of their neighbors Mn 8 O 12 H 8 and Ni 8 O 12 H 8 are ferrimagnetic and ferromagnetic, respectively. Hydrogenation leads to a decrease in the average binding energy per atom when moving across the 3 d ‐metal atom series. © 2018 Wiley Periodicals, Inc.