Premium
Chirality and spin density: Ab initio and density functional approaches
Author(s) -
Fluekiger P.,
Weber J.,
Chiarelli R.,
Rassat A.,
Ellinger Y.
Publication year - 1993
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560450614
Subject(s) - chemistry , density functional theory , spin density , spin (aerodynamics) , ab initio , ab initio quantum chemistry methods , adamantane , molecular physics , molecule , computational chemistry , condensed matter physics , physics , thermodynamics , organic chemistry
The spin distribution in a stable nitroxide biradical that shows ferromagnetic interactions in the solid phase has been studied at three levels of theory: First, at the UHF level; then, including correlation effects in UMP 2 calculations; and finally, the results are compared with the spin density obtained using the local density functional ( LDF ) approximation. It is shown that LDF spin densities are closer to UMP 2 than to UHF predictions; the difference between the UHF and the ( UMP 2, LDF ) results points to a redistribution of the spin repartition between N and O due to electronic correlation. For planar conformations of the NO group, there is symmetric distribution ( D 2d ) of the spin density on the adamantane skeleton. For nonplanar nitroxides, the molecule is chiral ( C 2 ), which results in a breakdown of the spin transmission on part of the adamantane cage. © 1993 John Wiley & Sons, Inc.