Journal
JOURNAL OF PHYSICAL CHEMISTRY B
Volume 119, Issue 24, Pages 7491-7502Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp511220x
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Funding
- NSF [CHE-1112560, CHE-1152533]
- NASA [NNX12AG77G]
- M. J. Murdock Charitable Trust
- Italian Ministero dell'Istruzione, dell'Universita e della Ricerca (MIUR) [PRIN-2010ERFKXL, FIRB-RBFR08DUX6-003]
- French Agency for Research Grant [ANR-12-BS08-0001-01]
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1507813, 1112560] Funding Source: National Science Foundation
- NASA [19662, NNX12AG77G] Funding Source: Federal RePORTER
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Femtosecond time-resolved IR spectroscopy is used to investigate the excited-state dynamics of a dinucleotide containing an 8-oxoguanine anion at the 5'-end and neutral adenine at the 3'-end. UV excitation of the dinucleotide transfers an electron from deprotonated 8-oxoguanine to its pi-stacked neighbor adenine in less than 1 ps, generating a neutral 8-oxoguanine radical and an adenine radical anion. These species are identified by the excellent agreement between the experimental and calculated IR difference spectra. The quantum efficiency of this ultrafast charge shift reaction approaches unity. Back electron transfer from the adenine radical anion to the 8-oxguanine neutral radical occurs in 9 Ps, or approximately 6 times faster than between the adenine radical anion and the 8-oxoguanine radical cation (Zhang, Y. et al. Proc. Natl. Acad. Sci. U.S.A. 2014, 111, 11612-11617). The large asymmetry in forward and back electron transfer rates is fully rationalized by semiclassical nonadiabatic electron transfer theory. Forward electron transfer is ultrafast because the driving force is nearly equal to the reorganization energy, which is estimated to lie between 1 and 2 eV. Back electron transfer is highly exergonic and takes place much more slowly in the Marcus inverted region.
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