Abstract
Thionated nucleobases have drawn considerable attention due to their role in medical treatment and biology, which triggered studies of their photophysics and photochemistry using various experimental and theoretical techniques. In particular, vacuum ultraviolet (VUV)-induced dissociative photoionization of 2-thiouracil (2-TU) has been recently studied using synchrotron radiation [Robinson et al., Molecules 2023, 28, 2354]. Here, using molecular dynamics simulations at the semiempirical OM2 level, we study the fragmentation dynamics of the cations of 2-TU and its isomer, 4-thiouracil (4-TU). Considering various VUV photon energies, we calculate energy-resolved mass spectra and breakdown diagrams for 2-TU and 4-TU. Remarkably, we find that the major fragments are different between the two compounds: 69 amu (C(3)NH(3)O(+)) for 2-TU and 85 amu (C(3)NH(3)S(+)) for 4-TU. Our simulations provide direct mechanistic insight into this observation and the fragmentation processes of thionated uracils in general.