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We present a comparative study of the gas-phase UV spectra of uracil and its thionated counterparts (2-thiouracil, 4-thiouracil and 2,4-dithiouracil), closely supported by time-dependent density functional theory calculations to assign the transitions observed. We systematically discuss pure gas-phase spectra for the (thio)uracils in the range of 200-400 nm (similar to 3.2-6.4 eV), and examine the spectra of all four species with a single theoretical approach. We note that specific vibrational modelling is needed to accurately determine the spectra across the examined wavelength range, and systematically model the transitions that appear at wavelengths shorter than 250 nm. Additionally, we find in the cases of 2-thiouracil and 2,4-dithiouracil, that the gas-phase spectra deviate significantly from some previously published solution-phase spectra, especially those collected in basic environments.
Quantum dynamics of the photoinduced charge separation in a symmetric donor-acceptor-donor triad
(2022)
The photoinduced charge separation in a symmetric donor-acceptor-donor (D-A-D) triad is studied quantum mechanically using a realistic diabatic vibronic coupling model. The model includes a locally excited DA*D state and two charge-transfer states D(+)A(-)D and DA(-)D(+) and is constructed according to a procedure generally applicable to semirigid D-A-D structures and based on energies, forces, and force constants obtained by quantum chemical calculations. In this case, the electronic structure is described by time-dependent density functional theory, and the corrected linear response is used in conjunction with the polarizable continuum model to account for state-specific solvent effects. The multimode dynamics following the photoexcitation to the locally excited state are simulated by the hybrid Gaussian-multiconfigurational time-dependent Hartree method, and temperature effects are included using thermo field theory. The dynamics are connected to the transient absorption spectrum obtained in recent experiments, which is simulated and fully assigned from first principles. It is found that the charge separation is mediated by symmetry-breaking vibrations of relatively low frequency, which implies that temperature should be accounted for to obtain reliable estimates of the charge transfer rate.