Evaluation of electron affinities of quinone derivatives by density functional theory

Nafikova, E. P.; Asfandiarov, N. L.; Kalimullina, L. R.; El’kin, Yu. N.

doi:10.1007/s11172-014-0475-0

Cited by 1 publication

(1 citation statement)

References 26 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The EA determines the function of the quinone in electron transfer and also forms the basis for computing reduction potentials, for which additional energetic contributions need to be considered. The computational prediction of quinone electron affinities and reduction potentials has received much attention, usually in system‐specific studies . Although approaches such as the equations‐of‐motion (EOM) or Green's function methods provide a direct way to obtain electron affinities for multiple electron attached states in a single calculation, quinone EAs are typically computed through differences of energies obtained by separate quantum chemical calculations of the quinone and the semiquinone radical.…”

Section: Introductionmentioning

confidence: 99%

Systematic High‐Accuracy Prediction of Electron Affinities for Biological Quinones

2018

View full text Add to dashboard Cite

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 domainbased 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 LPNObased extrapolation of correlation energy proves to be the most accurate approach. Methods that offer comparable performance are the parameterized LPNO-pCCSD, the DLPNO-CCSD(T 0 ), 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.

show abstract

Section: Introductionmentioning

confidence: 99%