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The Conceptual Dilemma of the One‐Electron Picture in Describing the Uniaxial Magnetism at Linear Coordination Sites
Author(s) -
Koo HyunJoo,
Kasapbasi Esra E.,
Whitten Jerry L.,
Whangbo MyungHwan
Publication year - 2019
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201900370
Subject(s) - magnetism , chemistry , electron , ion , symmetry (geometry) , spin (aerodynamics) , condensed matter physics , spin states , atomic physics , crystallography , physics , quantum mechanics , geometry , thermodynamics , inorganic chemistry , mathematics , organic chemistry
High‐spin Fe 2+ , Fe + and Co 2+ ions at linear two‐coordination sites exhibit uniaxial magnetism. In the one‐electron picture, the uniaxial magnetism of the Fe 2+ ion is explained, while those of the Fe + and Co 2+ ions are not, if the d‐state split pattern is 1e < 2e < 1a. The opposite is true if the d‐state split pattern is 1a < 1e < 2e. We resolved this conceptual dilemma by evaluating the relative stabilities for the various L states of linear molecules (Fe L 2 ) 0 , (Fe L 2 ) – , and (Co L 2 ) 0 with L = C(SiH 3 ) 3 on the basis of first‐principles broken‐symmetry and configuration interaction calculations. In the first‐principles picture, the total energy of an electron configuration depends not only on the energy sequence of the occupied d‐states, as do the one‐electron picture, but also on the electron repulsion between occupied d‐states, which is neglected by the one‐electron picture.