Homo vs lumo3/11/2023 ![]() The parent, we have investigated the electronic configurations ofĪ variety of one-electron oxidized DNA base analogues and their deprotonated (MOs) of one-electron oxidized molecule may rearrange from that of Because it is well known that molecular orbitals ![]() 11, 14− 19 The nature of the electronic configurations of these radical species Of the radical and its nature (σ- or π-type). Often aided by theory which were mainly limited to the identification Often show SOMO–HOMO inversion, which is not significantlyĮlectron paramagnetic resonance (EPR) and pulse radiolysis experiments Show that single-ring DNA base radicals formed by one-electron oxidationĪnd even small diatomic anion radicals formed by one-electron reduction Radicals or radicals with multiple ring systems. Have thus focused on SOMO–HOMO level inversion in distonic Various DFT methods, ab initio complete active space self-consistentįield (CASSCF), and MP2. 11, 12 In our work, SOMO–HOMOĮnergy level switching induced by inter base proton transfer in canonicalĭNA base pairs was found to be predicted by ab initio approaches including Proposed the SOMO–HOMO energy level inversion in deprotonatedĭNA/RNA base radicals, although these orbital inversions were found Level switching in several distonic radical anions and they, also, Initio multiconfigurational self-consistent field (MCSCF) and densityįunctional theory (DFT) methods to show the pH-induced SOMO–HOMO 2− 13 Recently, Coote and co-workers 11− 13 extensively used ab SOMO is found to be energetically lower in energy than the doubly The violation of the aufbau principle for distonic radicals in which 1 In recent years, several studies pointed out Orbital (SOMO) should be the highest occupied molecular orbital (HOMO). Of free radicals (odd electron systems), the singly occupied molecular To the aufbau principle, which states that “a maximum of twoĮlectrons are put into orbitals in the order of increasing orbitalĮnergy: the lowest-energy orbitals are filled before electrons are Yield new insights into the properties of free radical systems.Ĭonfiguration of an atom or molecule conforms Radicals and the orbital inversions vanish in water. Radicals and in contrast with those reported for distonic radicalĪnions in which SOMO–HOMO gaps are smaller for more localized Oxidation of aqueous superoxide anion producing triplet molecular Level inversion, one-electron oxidation takes place from HOMO notįrom the SOMO, which produces a molecule in its triplet ground state. The greater the gap between HOMO and SOMO. On a single atom (carbon, nitrogen, oxygen, sulfur, or selenium), (ii) The more localized spin density in σ-orbital Radicals produced by one-electron oxidation or reduction of natural-DNAīases, bromine-, sulfur-, selenium-, and aza-substituted DNA bases,Īs well as 20 diatomic molecules, we highlight the following importantįindings: (i) SOMO–HOMO level inversion is a common phenomenon From the extensive study of the electronic configurations of The integral equation formalism of the polarized continuum model solvation The B3LYP/6-31++G** method, with the inclusion of aqueous phase via The electronic configurations are calculated employing More doubly occupied molecular orbitals (MOs) (SOMO–HOMO level Such as superoxide anion radical to one-electron oxidized DNA relatedīase radicals that show the SOMO is energetically lower than one or In this study, weĬonsidered a number of radicals from smallest diatomic anion radicals Orbital (HOMO), but this is not the case always. Singly occupied molecular orbital (SOMO) ofĪ radical species is considered to be the highest occupied molecular
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