Extended Car-Parrinello molecular dynamics and electronic g-tensors study of benzosemiquinone radical anion
Copyright 2005 John Wiley & Sons, Ltd
| Veröffentlicht in: | Magnetic resonance in chemistry : MRC. - 1985. - 43 Spec no.(2005) vom: 15. Nov., Seite S237-47 |
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| Weitere Verfasser: | , |
| Format: | Aufsatz |
| Sprache: | English |
| Veröffentlicht: |
2005
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| Zugriff auf das übergeordnete Werk: | Magnetic resonance in chemistry : MRC |
| Schlagworte: | Journal Article |
| Zusammenfassung: | Copyright 2005 John Wiley & Sons, Ltd Car-Parrinello molecular dynamics simulations of benzoquinone and benzosemiquinone radical anion in both aqueous solution and the gas phase have been carried out at ambient conditions. Hydrogen bonding is considerably more extensive to the anionic than to the neutral aqueous system. In addition to the conventional hydrogen bonding to the carbonyl oxygen atoms, T-stacked hydrogen bonding to the pi-system is statistically and energetically significant for the semiquinone anion but not for the neutral quinone. EPR g-tensors have been calculated at DFT level for snapshots taken at regular intervals from the gas-phase and solution semiquinone anion trajectories. Different criteria for extraction of semiquinone/water clusters from the solution trajectory give insight into the effects of different interactions on the g-tensor, as does correlation of the g-tensor with statistically significant hydrogen-bond configurations identified along the trajectories. Comparison of gas-phase and solution results indicates opposite directions of direct electronic and indirect structural influences of hydrogen bonding on g-tensors. Short-time oscillations in g(x) along the trajectory are due mainly to C-O bond vibrations |
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| Beschreibung: | Date Completed 22.12.2005 Date Revised 24.10.2005 published: Print Citation Status PubMed-not-MEDLINE |
| ISSN: | 1097-458X |