Static and dynamic structures of halogenated dimethyl ether radical cations: An EPR and MO study

Itagaki, Yoshiteru; Wang, Peng; Isamoto, Nobuyuki; Shiotani, Masaru; Hasegawa, Akinori; Jansson, Magnus; Lunell, Sten

doi:10.1039/b200437b

Cited by 4 publications

(4 citation statements)

References 16 publications

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“…In contrast to this result, in the following paper we present a similar investigation on a mono-chlorinated DME + , CH 3 OCH 2 Cl + , which possesses an unpaired electron in a nonbonding orbital of the oxygen. 8…”

Section: Introductionmentioning

confidence: 99%

EPR spectra and structure of bis-chlorinated dimethyl ether radical cation, CH2ClOCH2Cl+

Itagaki

Wang

Shiotani

et al. 2002

Phys. Chem. Chem. Phys.

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The EPR spectrum of the CH 2 ClOCH 2 Cl + radical cation, generated by ionizing radiation in a halocarbon matrix at 77 K, consists of a major septet due to two equivalent Cl nuclei and an additional triplet due to two protons in the terminal CH 2 Cl groups. This assignment was confirmed using CD 2 ClOCD 2 Cl + . Theoretical calculations were performed to obtain the optimized geometries and theoretical hyperfine coupling constants (hfcc) for CH 2 ClOCH 2 Cl + using density functional theory (DFT). The results suggested Structures I (with C s symmetry) and II (with C 2 symmetry), where the two Cl, two C and one oxygen atoms make a five-membered ring and the unpaired electron is largely and equally shared by the two Cl nuclei. A reasonable magnitude in the proton coupling was obtained only for Structure I, having an energy lower than that of Structure II. The results were compared with those in our previous study on Cl(CH 2 ) 3 Cl + , giving similar EPR spectra. For Cl(CH 2 ) 3 Cl + , a geometry corresponding to Structure II was suggested from the proton coupling calculated by the CNDO/2 method. In this study, we reexamined the calculation by the DFT method and reached the conclusion that Cl(CH 2 ) 3 Cl + preferred a structure corresponding to Structure I.

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Section: Introductionmentioning

confidence: 99%

EPR spectra and structure of bis-chlorinated dimethyl ether radical cation, CH2ClOCH2Cl+

Itagaki

Wang

Shiotani

et al. 2002

Phys. Chem. Chem. Phys.

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“…(iv) quantum mechanical models for the calculation of energies, state functions, electron and spin densities [100,101,102], calculations of the spin-Hamilton operator under consideration of perturbation terms, solution of the time-independent Schrödinger equation considering isotope effects.…”

Section: Electron Spin Resonance (Esr) and Relations To Isotope Efmentioning

confidence: 99%

“…The influence of the 2 H substitution onto the conformation and rotation of the CH 3 groups in the dimethylether cation could be shown by Itagaki et al . [101]. The 1 H hyperfine constant showed up to 100 K nearly no temperature dependency different to the 2 H system because of the difference in the zero-point vibrations of the different rotational conformers.…”

Section: Selected Examplesmentioning

confidence: 99%

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Isotope Effects in ESR Spectroscopy

Stößer

Herrmann

2013

Molecules

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In order to present the relationship between ESR spectroscopy and isotope effects three levels are considered: (i) ESR spectroscopy is described on a general level up to the models for interpretation of the experimental spectra, which go beyond the usually used time and mass independent spin-Hamilton operator, (ii) the main characteristics of the generalized isotope effects are worked out, and finally (iii) the basic, mainly quantum mechanical effects are used to describe the coupling of electron spins with the degrees of freedom, which are accessible under the selected conditions, of the respective paramagnetic object under investigation. The ESR parameters and the respective models are formalized so far, that they include the time and mass depending influences and reflect the specific isotope effects. Relations will be established between the effects in ESR spectra to spin relaxation, to spin exchange, to the magnetic isotope effect, to the Jahn-Teller effects, as well as to the influence of zero-point vibrations. Examples will be presented which demonstrate the influence of isotopes as well as the kind of accessible information. It will be differentiated with respect to isotope effects in paramagnetic centres itself and in the respective matrices up to the technique of ESR imaging. It is shown that the use of isotope effects is indispensable in ESR spectroscopy.

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EPR Studies of Radical Ions Produced by Radiolysis of Fluorinated Hydrocarbons and Related Compounds in Solid Media

Shiotani

Komaguchi

2014

Applications of EPR in Radiation Research

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Static and dynamic structures of halogenated dimethyl ether radical cations: An EPR and MO study

Cited by 4 publications

References 16 publications

EPR spectra and structure of bis-chlorinated dimethyl ether radical cation, CH2ClOCH2Cl+

EPR spectra and structure of bis-chlorinated dimethyl ether radical cation, CH2ClOCH2Cl+

Isotope Effects in ESR Spectroscopy

EPR Studies of Radical Ions Produced by Radiolysis of Fluorinated Hydrocarbons and Related Compounds in Solid Media

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