We applied quantum mechanics/classical mechanics simulations to study excess-electron attachment and ionization of uridine monophosphate anion(d UMP-)in explicit aqueous solutions.We calculated vertical electron affin...We applied quantum mechanics/classical mechanics simulations to study excess-electron attachment and ionization of uridine monophosphate anion(d UMP-)in explicit aqueous solutions.We calculated vertical 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 d UMP^(-).The converged mean VEA(-0.31 e V)and AEA(2.13 e V)suggest that excess-electron can easily attach to d UMP^(-).The mean vertical(-0.50 e)and adiabatic(-0.62 e)excess-electron on uracil reveal that main excesselectrons 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 d UMP^(2-)dianion.The VDE value(2.78 e V)indicates that d UMP2-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.展开更多
基金supported by the National Natural Science Foundation of China(No.22173014,No.21773226,and No.21873100)Open Fund of the State Key Laboratory of Molecular Reaction Dynamics in Dalian Institute of Chemical Physics,Chinese Academy of Sciences。
文摘We applied quantum mechanics/classical mechanics simulations to study excess-electron attachment and ionization of uridine monophosphate anion(d UMP-)in explicit aqueous solutions.We calculated vertical 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 d UMP^(-).The converged mean VEA(-0.31 e V)and AEA(2.13 e V)suggest that excess-electron can easily attach to d UMP^(-).The mean vertical(-0.50 e)and adiabatic(-0.62 e)excess-electron on uracil reveal that main excesselectrons 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 d UMP^(2-)dianion.The VDE value(2.78 e V)indicates that d UMP2-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.
