| Abstract: | Thionucleobases can be used in chemoradiation therapy of cancer. Shape resonances (SRs) and core‐excited resonances (CERs) can lead to fragmentation and eventually result in strand breaks of DNA. In particular, the more energetic CERs are believed to cause double‐strand breaks that can hardly be repaired. In this work, both the SRs and CERs of exemplary 2‐thiouracil, 4‐thiouracil, 2‐thiothymine, 4‐thiothymine, and 6‐aza‐2‐thiothymine are investigated using stabilization method in conjunction with long range corrected time‐dependent density functional theory. Results indicate that the energies of (1) π*1 and π*2 SRs, (2) n‐π* CERs, and (3) mixed resonances of π‐π* CERs with π* SRs can be significantly stabilized due to thionation of uracil or thymine. It is noteworthy that the resonant cases of (2) and (3) can be accessed by electrons even at energies below 4 eV. Consequently, the increased decay of temporary anions can enhance strand breaks of DNA. |
