Premium
The electron‐spin magnetic moments ( g ‐factors) of C 2 − , N 2 − , O 2 − , and F 2 − and corresponding M + X 2 − radicals (M=alkali metal)
Author(s) -
Bruna Pablo J.,
Grein Friedrich
Publication year - 2000
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/(sici)1097-461x(2000)76:3<447::aid-qua13>3.0.co;2-n
Subject(s) - radical , chemistry , alkali metal , spin (aerodynamics) , excited state , electron , ab initio , magnetic moment , ab initio quantum chemistry methods , metal , ground state , atomic physics , computational chemistry , condensed matter physics , molecule , thermodynamics , physics , organic chemistry , quantum mechanics
Trends in the electron‐spin magnetic moments ( g factors) of the anions C 2 − , N 2 − , O 2 − , and F 2 − as stabilized in MX 2 radicals (M=alkali metal) are discussed on the basis of rules governing the magnetic coupling and MO theory. These expectations are compared with experimental data and our own ab initio results for M=Li, Na. For the σ‐radicals MC 2 and MF 2 , the component Δ g ‖ (parallel to the XX bond) is expected to be slightly negative, while the corresponding in‐plane [Δ g ⟂ ( i )] and out‐of‐plane [Δ g ⟂ ( o )] perpendicular components are of a few thousand ppm (ppm=10 −6 ). For the π‐radicals MN 2 and MO 2 , Δ g ‖ is of large magnitude but the Δ g ⟂ components are small. Both calculated and experimental g ‐shifts for MN 2 , MO 2 , and MF 2 agree with the predicted trends, whereas those for MC 2 (ground state) do not. However, good agreement of theoretical with experimental results is obtained when one considers the excited state 1 2 B 1 of MC 2 as carrier of the g shifts, rather than the X 2 A 1 state. © 2000 John Wiley & Sons, Inc. Int J Quant Chem 76: 447–457, 20000