Systematic High‐Accuracy Prediction of Electron Affinities for Biological Quinones.

Quinones play vital roles as electron carriers in fundamental biological processes; therefore, the ability to accurately predict their electron affinities is crucial for understanding their properties and function. The increasing availability of cost‐effective implementations of correlated wave function methods for both closed‐shell and open‐shell systems offers an alternative to density functional theory approaches that have traditionally dominated the field despite their shortcomings. Here, we define a benchmark set of quinones with experimentally available electron affinities and evaluate a range of electronic structure methods, setting a target accuracy of 0.1 eV. Among wave function methods, we test various implementations of coupled cluster (CC) theory, including local pair natural orbital (LPNO) approaches to canonical and parameterized CCSD, the domain‐based DLPNO approximation, and the equations‐of‐motion approach for electron affinities, EA‐EOM‐CCSD. In addition, several variants of canonical, spin‐component‐scaled, orbital‐optimized, and explicitly correlated (F12) Møller–Plesset perturbation theory are benchmarked. Achieving systematically the target level of accuracy is challenging and a composite scheme that combines canonical CCSD(T) with large basis set LPNO‐based extrapolation of correlation energy proves to be the most accurate approach. Methods that offer comparable performance are the parameterized LPNO‐pCCSD, the DLPNO‐CCSD(T0), and the orbital optimized OO‐SCS‐MP2. Among DFT methods, viable practical alternatives are only the M06 and the double hybrids, but the latter should be employed with caution because of significant basis set sensitivity. A highly accurate yet cost‐effective DLPNO‐based coupled cluster approach is used to investigate the methoxy conformation effect on the electron affinities of ubiquinones found in photosynthetic bacterial reaction centers. © 2018 Wiley Periodicals, Inc. A set of biologically relevant quinones with experimentally known electron affinities was compiled to evaluate the predictive ability of a range of wave function and density functional methods. Particular emphasis is placed on the performance characteristics of modern approximations to coupled cluster theory, which hold the promise of delivering systematically and consistently high accuracy for ever larger and chemically diverse systems. [ABSTRACT FROM AUTHOR]