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. 2022 Jun 9;7(24):20800-20808.
doi: 10.1021/acsomega.2c01331. eCollection 2022 Jun 21.

Benchmark Density Functional Theory Approach for the Calculation of Bond Dissociation Energies of the M-O2 Bond: A Key Step in Water Splitting Reactions

Naveen Kosar  1 , Khurshid Ayub  2 , Mazhar Amjad Gilani  3 , Shabbir Muhammad  4 , Tariq Mahmood  2
Affiliations

Benchmark Density Functional Theory Approach for the Calculation of Bond Dissociation Energies of the M-O2 Bond: A Key Step in Water Splitting Reactions

Naveen Kosar et al. ACS Omega. .

Abstract

A very fascinating aspect in quantum chemical research is to determine the accurate and cost-effective methods for the calculation of electronic and structural properties through a benchmark study. The current study focuses on the performance evaluation of density functional theory methods for the accurate measurement of bond dissociation energies (BDEs) of chemically important M-O2 bonds in water splitting reactions. The BDE measurement has got noteworthy attention due to its importance in all areas of chemistry. For BDE measurements of M-O2 bonds in five metal complexes with oxygen molecules, 14 density functionals (DFs) are chosen from seven classes of DFs with two series of mixed basis sets. A combination of pseudopotential and Pople basis sets [LANL2DZ & 6-31G(d) and SDD & 6-31+G(d)] are used as a series of mixed basis sets. The B3LYP-GD3BJ functional with LANL2DZ & 6-31G(d) gives outstanding results due to low deviations, error, and the best Pearson's correlation (R) between the experimental and theoretical data. Our study suggested an efficient, low-cost, precise, and accurate B3LYP-GD3BJ/LANL2DZ & 6-31G(d) level of theory for BDE of the M-O2 bond, which may be useful for chemists working in the field of energy generation and utilization.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Catalytic water oxidation and oxygen molecule evolution mechanism by Ru complexes.
Figure 2
Figure 2
RMSD of different DFs with two series of basis sets for M–O2 BDEs.
Figure 3
Figure 3
SD of different DFs with two series of basis sets for M–O2 BDEs.
Figure 4
Figure 4
MAE of different DFs with two series of basis sets for M–O2 BDEs.
Figure 5
Figure 5
Pearson’s correlation (R) of B3LYP-GD3Bj with SDD & 6-31+G(d) basis set for BDE calculation of the M–O2 bond.
Figure 6
Figure 6
Structures of transition-metal complexes having oxygen molecule with known experimental BDEs of M–O2 bond. In all the complexes, O2 show side on the binding model with selected transition-metal complexes.
Figure 7
Figure 7
Modal reaction for M–O2 bond dissociation of the rhenium-based complex with oxygen molecule. The rest of the complexes follow the same pattern.
See this image and copyright information in PMC

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