title: An ESR and ENDOR study of irradiated 6Li-formate.
abstract: Lithium formate ((6)LiOOCH.H(2)O), 95% (6)Li enrichment, combined with an exchange of crystallization water with D(2)O was investigated. The ESR spectrum of the radiation induced free radicals stable at room temperature consists of a singlet with a narrow line width, 0.92mT. (6)Li has smaller magnetic moment and nuclear spin, which resulted in the narrower line width accompanied with an increase in peak amplitude. In comparison with lithium formate with natural isotopic composition, (6)Li (7.5%, I=1) and (7)Li (92.5%, I=3/2), the sensitivity was increased by a factor of two. With optimised spectrometer settings (6)Li formate had seven times higher sensitivity compared to alanine. Therefore this material is proposed as a dosimeter material in a dose range down to 0.1Gy. The g and the (13)C-hyperfine (hf) tensors of the CO(2)(-) radical anion, major paramagnetic products, were evaluated to be g=(2.0037, 1.9975, 2.0017), and A((13)C)=(465.5, 447.5, 581.3) MHz for polycrystalline samples at room temperature. Furthermore, the (1)H-hf and (6)Li-hf tensors observed for the surroundings of CO(2)(-) by ENDOR technique were in fairly good agreement with DFT calculations. The CO(2)(-) radicals are found to be so stable that the formate is applicable to the ESR dosimetry, because of fully relaxing in a fully relaxed geometrical structure of the CO(2)(-) component and remaining tight binding with the surroundings after the H atom detachment from HCO(2)(-).
authors.affiliation: Graduate School of Engineering, Hiroshima University, Higashi-Hiroshima 739-8527, Japan. okoma@hiroshima-u.ac.jp
authors.forename: K
authors.initials: K
authors.lastname: Komaguchi
authors.forename: Y
authors.initials: Y
authors.lastname: Matsubara
authors.forename: M
authors.initials: M
authors.lastname: Shiotani
authors.forename: H
authors.initials: H
authors.lastname: Gustafsson
authors.forename: E
authors.initials: E
authors.lastname: Lund
authors.forename: A
authors.initials: A
authors.lastname: Lund
mesh_terms: D004307:Dose-Response Relationship, Radiation; D004578:Electron Spin Resonance Spectroscopy; D005561:Formates / Q000737:chemistry / Q000528:radiation effects*; D005609:Free Radicals / Q000528:radiation effects; D005720:Gamma Rays; D013696:Temperature; D013997:Time Factors
chemical_list: D005561:Formates; D005609:Free Radicals; C030544:formic acid