## 3 Results
### Charge and Spin Distribution Analysis  
The spatial geometry of the radical cations of the molecules discussed above indicates that differences in their spin and charge distribution and that of native nucleosides should be observed. All vertical and adiabatic energies of the positively charged forms were investigated at the M06-2X/6-31++G** level of theory in the condensed (aqueous) phase. The charge and spin distributions were analysed according to [PERSON]'s methodology [33]. The loss of the electron leads to the formation of a vertical radical cation state. The spin distribution analysis of positively charged 2\({}^{\prime}\)-deoxynucleoside analogues across sugar, base, and carbohydrate shows that a one-electron oxidising process occurs mainly on the nucleobase moiety, i.e., more than 60% (Table 2) in all of the discussed stages (the vertical cation in non-equilibrated and equilibrated solvent-solute modes and the adiabatic cation state, i.e., after system relaxation). Exceptions were noted in the cases of N2,3-\(\varepsilon\)-dGua, \(\varepsilon\)-dCyt, and H-\(\varepsilon\)-dCyt, in which the unpaired electron was finally localised (in almost 70% of cases) on the additional etheno part derived from LPO products, i.e., HNE. For the above molecules, the spin transfer from the nucleobase to the adduct moiety after structural and solvent relaxation was noted, i.e., \(\mathrm{VC}^{\mathrm{NE}}\rightarrow\mathrm{VC}^{\mathrm{EQ}}\rightarrow\mathrm{AC}\). The spin distribution analysis of the adiabatic cation state in the atom's course reveals that, for the discussed molecules, the atoms most prone to modification are as follows (the percentage of spin is given in parentheses): \(\varepsilon\)-dCyt: C8 (67); H-\(\varepsilon\)-dCyt: C8 (67); \(\varepsilon\)-dAde: C11 (34), N6 (30); H-\(\varepsilon\)-dAde: C11 (32), N6 (29); H-\(\varepsilon\)-dGua: N3 (16), O6 (16), C5 (15); (R)10-OH-PdGua: N3 (22), C5 (22), C8 (15); (S)10-OH-PdGua: N3 (22), C5 (22), C8 (15); M1-dGua: N3 (23), C5 (18), O6 (17), C8 (12); N1-\(\varepsilon\)-dGua: N3 (25), O6 (15), C10 (22); N2,3-\(\varepsilon\)-dGua: C10 (18), and C11 (53). In the case of HNE-dGuas, the following results were found to be dependent on the distribution of chiral centres (_C10, C12, and C13_): \(RRR\): N2 (32), C5 (15), C8 (15); \(RRS\): N2 (32), C5 (20), C8 (14); \(RSR\): C5 (22), O6 (20), C8 (15); \(RSS\): C5 (22), C8 (20), N3 (19); \(SRR\): N2 (31), C5 (21), C8 (15); \(SRS\): N2 (28), C5 (21), C8 (16); \(SSS\): C5 (22), C8 (20), and \begin{table}
\begin{tabular}{c c c c c c c c c c c} \hline \hline
**Compound** & **RMSD** & \(\mid\)**\(\Delta\)**DM**\(\mid\) & **Compound** & **RMSD** & \(\mid\)**\(\Delta\)**DM**\(\mid\) & & **Compound: (C10, C12, C13)** & **HNE-dGua** & \\ \hline
**dGua** & 0.043 & 3.54 & **H-\(\varepsilon\)-dCyt** & 0.474 & 0.92 & Chiral & RMSD & \(\mid\)\(\Delta\)**DM**\(\mid\) & Chiral & RMSD & \(\mid\)\(\Delta\)**DM**\(\mid\) \\ \hline
**dCyt** & 0.521 & 0.98 & \(\varepsilon\)-d**Ado** & 0.137 & 5.49 & \(RRR\) & 0.293 & 4.48 & \(SSS\) & 0.171 & 1.97 \\ \hline
**dAde** & 0.177 & 1.14 & **H-\(\varepsilon\)-dAdo** & 0.444 & 4.45 & \(RRS\) & 0.299 & 1.11 & \(SSR\) & 0.312 & 4.69 \\ \hline
**oxo**d**G**\({}^{\mathrm{SYN}}\) & 0.111 & 3.00 & **H-\(\varepsilon\)-dGua** & 0.205 & 1.15 & \(RSR\) & 0.481 & 4.48 & \(SRS\) & 0.344 & 2.29 \\ \hline
**R-OH-PdGua** & 0.213 & 1.86 & **N1-\(\varepsilon\)-dGua** & 0.275 & 0.73 & \(RSS\) & 0.502 & 3.21 & \(SRR\) & 0.156 & 1.80 \\ \hline
**S-OH-PdGua** & 0.226 & 2.26 & **N2,3-\(\varepsilon\)-dGua** & 0.650 & 5.49 & & & & & \\
**c-dCyt** & 0.254 & 3.05 & **M1-dGua** & 0.266 & 1.57 & & & & & \\ \hline \hline \end{tabular}
\end{table} 
Table 1: Root-mean-square deviation (RMSD) in [Å\({}^{2}\)] of atomic positions calculated for the discussed molecules (Figure 2) in their neutral and cationic ground states (cation versus neutral); the changes in dipole moment (DM) calculated after electron loss are given in Debyes [D] ( \(\mid\)\(\Delta\)**DM**\(\mid\) = DM(\(E_{0}^{0}\)) – DM(\(E_{0}^{+}\))). N3 (19).