Density functional theory calculations on Mössbauer parameters of nonheme iron nitrosyls.
Density Functional Theory (DFT) calculations on transition metal nitrosyls often reveal unusual spin density profiles, involving substantial spatial separation of majority and minority spin densities. Against this context, there is a significant lack of studies where DFT calculations have been quantitatively calibrated against experimental spectroscopic properties. Reported herein are DFT calculations of Mössbauer isomer shifts and quadrupole splittings for 21 nonheme iron complexes (26 distinct iron sites) including 9 iron nitrosyls. Low- (S = 1/2) and high-spin (S = 3/2) {FeNO}(7) complexes, S = 1/2 {Fe(NO)(2)}(9) species, and polynuclear iron nitrosyls are all represented within the set of compounds examined. The general conclusion with respect to isomer shifts is that DFT (OLYP/STO-TZP) performs comparably well for iron nitrosyls and for iron complexes in general. However, quadrupole splittings are less accurately reproduced for nitrosyl complexes.
Hopmann
Kathrin H
KH
Center for Theoretical and Computational Chemistry and Department of Chemistry, University of Tromsø, N-9037 Tromsø, Norway.
Ghosh
Abhik
A
Noodleman
Louis
L
D002245:Carbon Dioxide / Q000737:chemistry; D003198:Computer Simulation; D018360:Crystallography, X-Ray; D007501:Iron / Q000737:chemistry*; D008956:Models, Chemical; D015394:Molecular Structure; D009569:Nitric Oxide / Q000737:chemistry; D009589:Nitrogen Oxides / Q000737:chemistry*
D009589:Nitrogen Oxides; D002245:Carbon Dioxide; D009569:Nitric Oxide; C073661:dinitrosyl iron complex; D007501:Iron