| 1. |
- Komaguchi, K, et al.
(författare)
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An ESR and ENDOR study of irradiated 6Li-formate
- 2007
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Ingår i: Spectrochimica Acta Part A - Molecular and Biomolecular Spectroscopy. - : Elsevier BV. - 1386-1425 .- 1873-3557. ; 66:3, s. 754-760
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Tidskriftsartikel (refereegranskat)abstract
- Lithium formate (6LiOOCH·H2O), 95% 6Li enrichment, combined with an exchange of crystallization water with D2O was investigated. The ESR spectrum of the radiation induced free radicals stable at room temperature consists of a singlet with a narrow line width, 0.92 mT. 6Li 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, 6Li (7.5%, I = 1) and 7Li (92.5%, I = 3/2), the sensitivity was increased by a factor of two. With optimised spectrometer settings 6Li formate had seven times higher sensitivity compared to alanine. Therefore this material is proposed as a dosimeter material in a dose range down to 0.1 Gy. The g and the 13C-hyperfine (hf) tensors of the CO2- radical anion, major paramagnetic products, were evaluated to be g = (2.0037, 1.9975, 2.0017), and A(13C) = (465.5, 447.5, 581.3) MHz for polycrystalline samples at room temperature. Furthermore, the 1H-hf and 6Li-hf tensors observed for the surroundings of CO2- by ENDOR technique were in fairly good agreement with DFT calculations. The CO2- 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 CO2- component and remaining tight binding with the surroundings after the H atom detachment from HCO2-. © 2006 Elsevier B.V. All rights reserved.
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| 2. |
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| 3. |
- Sastry, M, et al.
(författare)
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51V(n,β)52Cr reaction for neutron dosimetry : Development and assessment of a spectrophotometric method for determination of Cr in vanadium at sub ppm level
- 2004
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Ingår i: Spectrochimica Acta Part A - Molecular and Biomolecular Spectroscopy. - : Elsevier BV. - 1386-1425 .- 1873-3557. ; 60:10, s. 2363-2367
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Tidskriftsartikel (refereegranskat)abstract
- With a view to monitoring the changes in coloration caused by the nuclear reaction 51V(n,β)52Cr in solution of vanadyl sulphate and using it for neutron dosimetry, electronic absorption spectra of vanadyl sulphate solutions were investigated at different concentrations of chromate impurity in micromolar range. It was observed that the presence of chromate enhances the absorptivity over a wide wavelength range serving essentially as a colouring agent for vanadium matrix, presumably due to charge transfer process. The absorbance at 380nm varied linearly over a wide concentration range. The limit of detection of chromate obtained is shown to be adequate for detecting neutron-induced chemical transmutation of vanadium to chromium under standard reactor conditions, when used with long path length cells. It was observed that the absorbance does not change on electron irradiation, suggesting that radiolytic effects due to beta decay, if any, do not interfere in the measurement of neutron-induced changes. In addition to its potential for neutron dosimetry, this is the first report of a simple and direct method of estimation of Cr in vanadium matrix at sub ppm level.
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| 4. |
- Danilczuk, M., et al.
(författare)
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Conduction electron spin resonance of small silver particles
- 2006
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Ingår i: Spectrochimica Acta Part A - Molecular and Biomolecular Spectroscopy. - : Elsevier BV. - 1386-1425 .- 1873-3557. ; 63:1, s. 189-191
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Tidskriftsartikel (refereegranskat)abstract
- Electron spin resonance (ESR) spectroscopy has been used to study the conduction electron spin resonance (CESR) of small silver particles stabilized in dehydrated Ag-rho zeolite. Silver particles were produced by hydrogen reduction at elevated temperatures and diameter of the stabilized particles was calculated based on the linewidth of CESR signal using Kawabata theory. © 2005 Elsevier B.V. All rights reserved.
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| 5. |
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| 6. |
- Komaguchi, K., et al.
(författare)
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ESR and theoretical studies of trimer radical cations of coronene
- 2006
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Ingår i: Spectrochimica Acta Part A - Molecular and Biomolecular Spectroscopy. - : Elsevier BV. - 1386-1425 .- 1873-3557. ; 63:1, s. 76-84
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Tidskriftsartikel (refereegranskat)abstract
- Highly resolved ESR spectra of monomer, dimer and trimer radical cations of coronene (C24H12) were observed at room temperature for a solution of 1,1,1,3,3,3-hexafluoro-2-propan-2-ol (HFP) containing thallium(III) trifluoroacetate as oxidant. The spectra consisting of multiple lines with isotropic 1H-hyperfine splitting (hfs) constants of 0. 0766 mT (24H) and 0.013 mT (6H) were attributable to a mixture of the dimer with the trimer radical cations, (C24H12)2+ and (C24H12)3+. For (C24H12)2+, the 1H-hfs constant agreed well with the reported value, 0.077 mT. However, for (C 24H12)3+, the values were significantly different from the reported ones, 0.117 mT (12H) and 0.020 mT (24H), by Ohya Nishiguchi et al. [H. Ohya-Nishiguchi, H. Ide, N. Hirota, Chem. Phys. Lett. 66 (1979) 581], but rather similar to those reported by Willigen et al. [H. van Willigen, E. De Boer, J.T. Cooper, W.F. Forbes, J. Chem . Phys. 49 (1968) 1190]. In conflict with Willigen's report, however, no ESR line broadening which has been ascribed to a low stationary concentration of (C 24H12)3+ was detected. Based on ab initio MO calculations for benzene as a compact model of C24H 12, the structure of (C24H12)3+ was investigated in terms of the observed 1H-hfs constants. A staggered sandwich C2v structure was suggested being at the "global" minimum for the benzene trimer cation. In the structure, the unpaired electron spin is predominantly localized to the central ring, which is qualitatively in agreement with the previous ESR results of (C 24H12)3+ by Ohya-Nishiguchi et al. In addition, as a "local" minimum, the benzene trimer was indicated to have a slipped sandwich Cs structure, which is less stable by ca. 19 kJ mol-1 than the "global" minimum. In this structure, the unpaired electron spin was nearly equally distributed on both the central and one of the two side C24H12 molecules. The observed 1H-hfs constants were possibly attributable to the (C 24H12)3+ cation with the analogous slipped sandwich Cs structure.
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| 7. |
- Liu, Wei, et al.
(författare)
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Geometric and electronic structure of the diphenylamine radical cation : An EPR, ENDOR and MO study
- 2005
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Ingår i: Journal of Molecular Structure. - : Elsevier BV. - 0022-2860 .- 1872-8014. ; 733:1-3, s. 13-17
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Tidskriftsartikel (refereegranskat)abstract
- The geometric and electronic structure of the diphenylamine radical cation Ph2(H)N+ obtained by X-irradiation of diphenylamine in CFCl3 at low temperature have been studied by the methods of EPR and ENDOR combined with theoretical calculations. The 110 K ENDOR spectrum of Ph2(H)N+ is mainly attributed to the ortho and meta phenyl ring protons. The accurate assignment of spectroscopic parameters is based on spectral simulations and theoretical calculations. Close agreement was obtained between the experimental and calculated hyperfine tensors of ortho and meta protons. © 2004 Elsevier B.V. All rights reserved.
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| 8. |
- LiU, Ya-Jun, et al.
(författare)
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Density functional theory study of NO adsorbed in A-zeolite
- 2005
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Ingår i: Journal of Physical Chemistry B. - : American Chemical Society (ACS). - 1520-6106 .- 1520-5207. ; 109:16, s. 7948-7951
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Tidskriftsartikel (refereegranskat)abstract
- Density functional theory was employed to investigate the adsorption site and hyperfine interactions of nitric oxide adsorbed in Na-LTA (previous name NaA) zeolite. Three different cluster models of increasing complexity were used to represent the zeolite network: (1) a six-membered ring terminated by hydrogen atoms with one sodium ion above the ring, (2) as model 1 with the addition of three sodium ions located at the centers of three imagined four-membered rings adjacent to the six-membered ring, and (3) as model 2 with the addition of the three four-membered rings adjacent to the six-membered ring. Calculations on the largest system (model 3) showed very good agreement with measured electronic Zeeman interaction couplings, 14N hyperfine coupling tensors, and 23Na hyperfine and nuclear quadruple coupling tensors of the S = 1/2 Na+⋯N-O adsorption complex when the position of the sodium ion was relaxed. The optimized geometry of the complex agreed nicely with that estimated experimentally, except for the Na-N distance, where the present results indicate that the distance deduced from previous ENDOR experiments may be underestimated by as much as 0.5 Å. © 2005 American Chemical Society.
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| 9. |
- Nuzhdin, K.B., et al.
(författare)
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Structure of radical cations of saturated heterocyclic compounds with two heteroatoms as studied by electron paramagnetic resonance, electron-nuclear double resonance, and density functional theory calculations
- 2005
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Ingår i: Journal of Physical Chemistry A. - : American Chemical Society (ACS). - 1089-5639 .- 1520-5215. ; 109:28, s. 6166-6173
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Tidskriftsartikel (refereegranskat)abstract
- The radical cations of piperazine, morpholine, thiomorpholine, and thioxane were investigated by electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) spectroscopy in a solid Freon matrix. Optimized geometry and magnetic parameters of the radical cations were calculated using a density functional theory (DFT)/Perdew-Burke-Ernzerhof (PBE) method. Both experimental and theoretical results suggest that all the studied species adopt chair (or distorted chair) conformations. No evidence for the boat conformers with intramolecular σ*-bonding between heteroatoms were obtained. In the cases of morpholine and thioxane, the oxygen atoms are characterized by relatively small spin populations, whereas a major part of spin density is located at N and S atoms, respectively. The thiomorpholine radical cation exhibits nearly equal spin population of N and S atoms. In most cases (except for thioxane), the calculated magnetic parameters agree with the experimental data reasonably well. © 2005 American Chemical Society.
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| 10. |
- Tachikawa, Hiroto, et al.
(författare)
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Structures and electronic states of trimer radical cations of coronene : DFT-ESR simulation study
- 2022
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry. - 1463-9076 .- 1463-9084. ; 24:17, s. 10318-10324
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Tidskriftsartikel (refereegranskat)abstract
- Coronene (C24H12), a charge transfer complex with low-cost and high-performance energy storage, has recently attracted attention as a model molecule of graphene nano-flakes (GNFs). The stacking structures of the trimer radical cation correlate strongly with the conduction states of the GNFs. In the present paper, the structures and electronic states of the monomer, dimer and trimer radical cations of coronene were investigated by means of density functional theory calculations. In particular, the proton hyperfine coupling constants of these species were determined. The radical cation of coronene(+) (monomer) showed two structures corresponding to the (2)A(u) and B-2(3u) states due to the Jahn-Teller effect. The (2)A(u) state was more stable than the B-2(3u) state, although the energy difference between the two states was only 0.03 kcal mol(-1). The dimer and trimer radical cations took stacking structures distorted from a full overlap structure. The intermolecular distances of the molecular planes were 3.602 angstrom (dimer) and 3.564 and 3.600 angstrom (trimer). The binding energies of the dimer and trimer were calculated to be 8.7 and 13.3 kcal mol(-1), respectively. The spin density was equivalently distributed on both coronene planes in the dimer cation. In contrast, the central plane in the trimer cation had a larger spin density, rho = 0.72, than the upper and lower planes, both with rho = 0.14. The proton hyperfine coupling constants calculated from these structures and the electronic states of the monomer, dimer, and trimer radical cations of coronene were in excellent agreement with previous ESR spectra of coronene radical cations. The structures and electronic states of (coronene)(n)(+) (n = 1-3) were discussed on the basis of the theoretical results.
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| 11. |
- Yahiro, H., et al.
(författare)
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Copper-phthalocyanine encapsulated into zeolite-Y with high Si/Al : An EPR study
- 2005
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Ingår i: Chemical Physics Letters. - : Elsevier BV. - 0009-2614 .- 1873-4448. ; 415:1-3, s. 126-130
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Tidskriftsartikel (refereegranskat)abstract
- Copper (II) phthalocyanine (CuPc) molecules encapsulated into zeolite-Y with Si/Al ratios of 2.7 and 410 were prepared by an in situ synthesis and characterized by UV-Vis and electron paramagnetic resonance (EPR) spectroscopies. Resolved Cu-hyperfine and N-superhyperfine structures were observed in the EPR spectrum of CuPc encapsulated into zeolite-Y with a high Si/Al ratio. UV-Vis and EPR studies as well as theoretical calculations suggest that the encapsulated CuPc molecule was distorted in zeolite-Y with keeping of the square-planar symmetry around the center copper (II) ion. © 2005 Elsevier B.V. All rights reserved.
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