MCSCF and DFT calculations of EPR parameters of sulfur centered radicals

Citation
M. Engstrom et al., MCSCF and DFT calculations of EPR parameters of sulfur centered radicals, CHEM P LETT, 328(4-6), 2000, pp. 483-491
Citations number
35
Language
INGLESE
art.tipo
Article
Categorie Soggetti
Physical Chemistry/Chemical Physics
Journal title
CHEMICAL PHYSICS LETTERS
ISSN journal
0009-2614 → ACNP
Volume
328
Issue
4-6
Year of publication
2000
Pages
483 - 491
Database
ISI
SICI code
0009-2614(20001006)328:4-6<483:MADCOE>2.0.ZU;2-A
Abstract
The EPR parameters of sulfur centered radicals are different depending on t he radical structure, charge and solvent. That is, the g- and A-tensor comp onents provide significant patterns which may distinguish sulfur radical st ructures from each other. In the present work, these EPR parameters were ca lculated for monosulfide radicals (RS'), disulfide radicals (RSS.), radical cations ((RSSR+)-S-.) and anions ((RSSR-)-S-.), with R = CH3, using the MC SCF linear response and DFT/B3LYP methods. Results were in agreement with e xperimental data for the cases when well-resolved EPR spectra are available . Especially, the assignment of the disulfide anion in ribonucleotide reduc tase was confirmed. The results indicate that investigations with the prese nt computational methods on refined structures and solvent modeling may pro vide interpretations of experimental data on unassigned radical species. (C ) 2000 Elsevier Science B.V. All rights reserved.