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Radiation products at 77 K in trehalose single crystals: EMR and DFT analysis

Mihaela Adeluta Tarpan UGent, Hendrik De Cooman UGent, Eli Olaug Hole, Michel Waroquier UGent and Freddy Callens UGent (2012) JOURNAL OF PHYSICAL CHEMISTRY A. 116(13). p.3377-3387
abstract
The radicals obtained in trehalose dihydrate single crystals after 77 K X-irradiation have been investigated at the same temperature using X-band electron paramagnetic resonance (EPR), electron nuclear double resonance (ENDOR), and ENDOR-induced EPR (EIE) techniques. Five proton hyperfine coupling tensors were unambiguously determined from the ENDOR measurements and assigned to three carbon-centered radical species (T1, T1*, and T2) based on the EIE spectra. EPR angular variations revealed the presence of four additional alkoxy radical species (T3 to T6) and allowed determination of their g tensors. Using periodic density functional theory (DFT) calculations, T1/T1*, T2, and T3 were identified as H-loss species centered at C4, C1', and O2', respectively. The T4 radical is proposed to have the unpaired electron at O4, but considerable discrepancies between experimental and calculated HFC values indicate it is not simply the (net) H-loss species. No suitable models were found for T5 and T6. These exhibit a markedly larger g anisotropy than T3 and T4, which were not reproduced by any of our DFT calculations.
Please use this url to cite or link to this publication:
author
organization
year
type
journalArticle (original)
publication status
published
subject
keyword
ALKOXY RADICALS, SPIN-RESONANCE, MAGNETIC-RESONANCE, FREE-RADICALS, PROTON HYPERFINE COUPLINGS, SPACE GAUSSIAN PSEUDOPOTENTIALS, ELECTRON-PARAMAGNETIC-RESONANCE, DENSITY-FUNCTIONAL THEORY, MOLECULAR-DYNAMICS, ROOM-TEMPERATURE
journal title
JOURNAL OF PHYSICAL CHEMISTRY A
J. Phys. Chem. A
volume
116
issue
13
pages
3377 - 3387
Web of Science type
Article
Web of Science id
000302337100006
JCR category
PHYSICS, ATOMIC, MOLECULAR & CHEMICAL
JCR impact factor
2.771 (2012)
JCR rank
10/34 (2012)
JCR quartile
2 (2012)
ISSN
1089-5639
DOI
10.1021/jp300979g
language
English
UGent publication?
yes
classification
A1
copyright statement
I have transferred the copyright for this publication to the publisher
id
2098741
handle
http://hdl.handle.net/1854/LU-2098741
date created
2012-05-04 11:10:54
date last changed
2012-05-07 10:26:55
@article{2098741,
  abstract     = {The radicals obtained in trehalose dihydrate single crystals after 77 K X-irradiation have been investigated at the same temperature using X-band electron paramagnetic resonance (EPR), electron nuclear double resonance (ENDOR), and ENDOR-induced EPR (EIE) techniques. Five proton hyperfine coupling tensors were unambiguously determined from the ENDOR measurements and assigned to three carbon-centered radical species (T1, T1*, and T2) based on the EIE spectra. EPR angular variations revealed the presence of four additional alkoxy radical species (T3 to T6) and allowed determination of their g tensors. Using periodic density functional theory (DFT) calculations, T1/T1*, T2, and T3 were identified as H-loss species centered at C4, C1', and O2', respectively. The T4 radical is proposed to have the unpaired electron at O4, but considerable discrepancies between experimental and calculated HFC values indicate it is not simply the (net) H-loss species. No suitable models were found for T5 and T6. These exhibit a markedly larger g anisotropy than T3 and T4, which were not reproduced by any of our DFT calculations.},
  author       = {Tarpan, Mihaela Adeluta and De Cooman, Hendrik and Hole, Eli Olaug and Waroquier, Michel and Callens, Freddy},
  issn         = {1089-5639},
  journal      = {JOURNAL OF PHYSICAL CHEMISTRY A},
  keyword      = {ALKOXY RADICALS,SPIN-RESONANCE,MAGNETIC-RESONANCE,FREE-RADICALS,PROTON HYPERFINE COUPLINGS,SPACE GAUSSIAN PSEUDOPOTENTIALS,ELECTRON-PARAMAGNETIC-RESONANCE,DENSITY-FUNCTIONAL THEORY,MOLECULAR-DYNAMICS,ROOM-TEMPERATURE},
  language     = {eng},
  number       = {13},
  pages        = {3377--3387},
  title        = {Radiation products at 77 K in trehalose single crystals: EMR and DFT analysis},
  url          = {http://dx.doi.org/10.1021/jp300979g},
  volume       = {116},
  year         = {2012},
}

Chicago
Tarpan, Mihaela Adeluta, Hendrik De Cooman, Eli Olaug Hole, Michel Waroquier, and Freddy Callens. 2012. “Radiation Products at 77 K in Trehalose Single Crystals: EMR and DFT Analysis.” Journal of Physical Chemistry A 116 (13): 3377–3387.
APA
Tarpan, M. A., De Cooman, H., Hole, E. O., Waroquier, M., & Callens, F. (2012). Radiation products at 77 K in trehalose single crystals: EMR and DFT analysis. JOURNAL OF PHYSICAL CHEMISTRY A, 116(13), 3377–3387.
Vancouver
1.
Tarpan MA, De Cooman H, Hole EO, Waroquier M, Callens F. Radiation products at 77 K in trehalose single crystals: EMR and DFT analysis. JOURNAL OF PHYSICAL CHEMISTRY A. 2012;116(13):3377–87.
MLA
Tarpan, Mihaela Adeluta, Hendrik De Cooman, Eli Olaug Hole, et al. “Radiation Products at 77 K in Trehalose Single Crystals: EMR and DFT Analysis.” JOURNAL OF PHYSICAL CHEMISTRY A 116.13 (2012): 3377–3387. Print.