2017
DOI: 10.1021/acs.jpcb.7b10002
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SOMO–HOMO Level Inversion in Biologically Important Radicals

Abstract: Conventionally, the singly occupied molecular orbital (SOMO) of a radical species is considered to be the highest occupied molecular orbital (HOMO), but this is not the case always. In this study, we considered a number of radicals from smallest diatomic anion radicals such as superoxide anion radical to one-electron oxidized DNA related base radicals that show the SOMO is energetically lower than one or more doubly occupied molecular orbitals (MOs) (SOMO–HOMO level inversion). The electronic configurations ar… Show more

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Cited by 62 publications
(60 citation statements)
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“…[30] We used time-dependent density functional theory (TD-DFT) to characterize the low-lying excited electronic states of the TAC radical dication 2.A sp redicted, [20] the two lowest-energy absorptions result from transitions from the nearly degenerate HOMOÀ1a nd HOMOÀ2o rbitals to the SOMO (Figure 4B). These transitions result in an excited-state SOMO-HOMO level inversion, [31] with the resulting hole residing in asub-frontier orbital. Theenergy gained from repopulation of this low-lying orbital helps to explain the exceptionally potent oxidizing power of this photoexcited species.…”
Section: Methodsmentioning
confidence: 99%
“…[30] We used time-dependent density functional theory (TD-DFT) to characterize the low-lying excited electronic states of the TAC radical dication 2.A sp redicted, [20] the two lowest-energy absorptions result from transitions from the nearly degenerate HOMOÀ1a nd HOMOÀ2o rbitals to the SOMO (Figure 4B). These transitions result in an excited-state SOMO-HOMO level inversion, [31] with the resulting hole residing in asub-frontier orbital. Theenergy gained from repopulation of this low-lying orbital helps to explain the exceptionally potent oxidizing power of this photoexcited species.…”
Section: Methodsmentioning
confidence: 99%
“…As predicted, the two lowest‐energy absorptions result from transitions from the nearly degenerate HOMO−1 and HOMO−2 orbitals to the SOMO (Figure B). These transitions result in an excited‐state SOMO–HOMO level inversion, with the resulting hole residing in a sub‐frontier orbital. The energy gained from repopulation of this low‐lying orbital helps to explain the exceptionally potent oxidizing power of this photoexcited species.…”
Section: Figurementioning
confidence: 99%
“…A series of papers was published in recent five years addressing the dissociative electron attachment to 2-thiouracil (2-TU) and 2-thiothymine in gas-phase and showing that the fragmentation of these molecules arises mainly at the sulfur site [35,36,37,38,39,40]. Some attention was also paid to electron paramagnetic resonance (EPR) studies [41,42,43,44,45,46,47,48,49] combined with DFT calculations [50,51,52] of radicals derived from γ-irradiated single crystals of sulfur-substituted nucleobases.…”
Section: Introductionmentioning
confidence: 99%