Temporary anion states of radiosensitive halopyrimidines: Shape and core-excited resonances

Transient Anions in Radiobiology and Radiotherapy: From Gaseous Biomolecules to Condensed Organic and Biomolecular Solids

“…The most striking evidence of a huge enhancement of LEE damage obtained upon Br substitution in thymine is seen in the early results of Klyachko et al [160], who found that, in the presence of water, DEA to bromouracil could be enhanced by orders of magnitude compared to the dry compound. Differences between wet and dry TMA states of halogenated pyrimidines have recently been investigated by Cheng et al [172]. They applied Koopman's theorem in the framework of long-range corrected density functional theory for calculation of the TMA states and self-consistent reaction field methods in a polarized continuum to account for the solvent.…”

Shape and core‐excited resonances of thionucleobases

“…In the S‐LC‐TDDFT method, E (η) is the difference between the total energy of vertical anion state and that of neutral ground state . The eigensolutions of SKT consist of SR and DC solutions; while in S‐LC‐TDDFT, they may contain SR, CER, mixture of SR and CER, DC, and the excitation of an electron to DC (E‐DC) solutions . As η varies, the eigenvalues of TAS solutions are relatively stable while those of DC/E‐DC solutions are not.…”

“…In basis set I, only the orbital exponents of “++” functions will be multiplied by η. Since our previous calculations have shown that this basis set is flexible enough to characterize the TASs of uracil and halopyrimidines, all of our stabilization computations will be based on basis set I. Basis set II denotes the 6–311G(d,p) basis set for H, C, N, and O atoms and the 6–311G(3d,p) basis set for S atom.…”

“…In the present study, ωB97XD of LC‐DFT in conjunction with the SKT (SKT ωB97XD) and TD‐ωB97XD of TDDFT in conjunction with SM (S‐TD‐ωB97XD) will be adopted due to their superior calculated AEs in the studies of various molecules . In addition, S‐EA SAC‐CI is also adopted for comparison.…”

“…By combining the aforementioned SM and LC potentials, we have introduced a stabilized Koopmans theory (SKT) in the framework of LC‐DFT in the study of SRs for various molecules . As for CERs, we have introduced the stabilized long range corrected time‐dependent density functional theory (S‐LC‐TDDFT) in the studies of p‐benzoquinone and halopyrimidines . In the case of halopyrimidines, the solvent effect of water has also been considered using polarized continuum model.…”