Performance of Frozen Density Embedding for Modeling Hole Transfer Reactions

TL;DR

This paper benchmarks the FDE-ET method for hole transfer reactions, identifying the most accurate computational setup with minimal error, and confirms its effectiveness for calculating diabatic couplings.

Contribution

It provides a comprehensive benchmark of FDE-ET with various functionals and basis sets, establishing optimal parameters for accurate hole transfer modeling.

Findings

PBE functional with PW91k and TZP basis set yields 7% error.

FDE-ET is effective for computing diabatic couplings.

Optimal computational setup identified for hole transfer calculations.

Abstract

We have carried out a thorough benchmark of the FDE-ET method for calculating hole transfer couplings. We have considered 10 exchange-correlation functionals, 3 non-additive kinetic energy functionals and 3 basis sets. Overall, we conclude that with a 7% mean relative unsigned error, the PBE functional coupled with the PW91k non-additive Kinetic energy functional and a TZP basis set constitutes the most stable, and accurate level of theory for hole-transfer coupling calculations. The FDE-ET method is found to be an excellent tool for computing diabatic couplings for hole transfer reactions.