We applied quantum mechan-ics/classical mechanics simula-tions to study excess-electron attachment and ionization of uridine monophosphate anion(dUMP-)in explicit aqueous solutions.We calculated verti-cal electron affinities(VEAs),adiabatic electron affinities(AEAs),vertical detachment energies(VDEs),vertical ionization energies(VIEs),and adiabatic ionization energies(AIEs)of the 40 structures obtained from molecular dynamic trajectory.The excess-electron and hole distributions were analyzed in electron attachment and ionization of aqueous dUMP-.The converged mean VEA(-0.31 eV)and AEA(2.13 eV)suggest that excess-electron can easily attach to dUMP-.The mean vertical(-0.50 e)and adiabatic(-0.62 e)excess-electron on uracil reveal that main excess-electrons are localized on nucleobases at the most snapshots.The distributions at several special snapshots demonstrate the excess-electron delocalization over nucleobases/ribose or ribose/phosphate group after the structural relaxations of dUMP2-dianion.The VDE value(2.78 eV)indicates that dUMP2-dianion could be very stable.Moreover,the mean VIE is 8.13 eV which is in agreement with the previous calculation using solvation model.The hole distributions on uracil suggest that the nucleobases are easily ionized after the irradiation of high-energy rays.In vertical ionizations,the holes would be delocalized over uracil and ribose at several snapshots.Observing the adiabatic hole distributions,it can be found that electrons on phosphate group and holes on nucleobases can be transferred to ribose at the special snapshots in the structural relaxation of neutral species.

Yan Zhang;Xuan-ning Chen;Shu-hui Yin;Song-qiu Yang

School of Science,Dalian Maritime University,Dalian 116026,China;State Key Laboratory of Molecular Reaction Dynamics,Dalian Institute of Chemical Physics,Chinese Academy of Science,Dalian 116023,China

化学物理学报（英文版）

[1]Yan Zhang;Xuan-ning Chen;Shu-hui Yin;Song-qiu Yang-.Excess-Electron Attachment and Ionization of Aqueous Uridine Monophosphate Anion)[J].化学物理学报（英文版）,2022(02):375-382

Monophosphate,dUMP,VEAs,AEAs,VDEs,VIEs,AIEs,VEA,nucleobases,dUMP2,dianion,ionizations

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