Efficient EOM-CC-based Protocol for the Calculation of Electron Affinity of Solvated Nucleobases: Uracil as a Case Study

We present an explicit solvation protocol for the calculation of electron affinity values of the solvated nucleobases. The protocol uses a quantum mechanics/molecular mechanics (QM/MM) approach based on the newly implemented domain-based pair natural orbital EOM-CCSD (equation-of-motion coupled-cluster single-double) method. The stability of the solvated nucleobase anion is sensitive to the local distribution of the water molecules around the nucleobase, and the calculated electron affinity values converge slowly with respect to the number of snapshots and the size of the water box. The use of nonpolarizable water molecules leads to an overestimation of the electron affinity and makes the result sensitive to the size of the QM region in the QM/MM calculation. The electron affinity values, although sensitive to the size of the basis set, lead to an almost constant blue shift of the electron affinity upon the increase in the basis set. The present protocol allows for a controllable description of the various parameters affecting the electron affinity value, and the calculated adiabatic electron affinity values are in excellent agreement with experimental results.

Automated summary

The research introduces an explicit solvation protocol for calculating the electron affinity values of solvated nucleobases. The study shows that the stability of solvated nucleobase anions is affected by the local distribution of water molecules, and the calculation of electron affinity values converges slowly with respect to the number of snapshots and size of the water box. The protocol allows for a controlled description of various parameters affecting the electron affinity value and yields adiabatic electron affinity values in excellent agreement with experimental results.