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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.
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References

    1. Shahbaz M.; Mutascu M.; Azim P. Environmental Kuznets Curve in Romania and the Role of Energy Consumption. Renewable Sustainable Energy Rev. 2013, 18, 165–173. 10.1016/j.rser.2012.10.012. - DOI
    1. Bard A. J.; Fox M. A. Artificial Photosynthesis: Solar Splitting of Water to Hydrogen and Oxygen. Acc. Chem. Res. 1995, 28, 141–145. 10.1021/ar00051a007. - DOI
    1. Chow J.; Kopp R. J.; Portney P. R. Energy Resources and Global Development. Science 2003, 302, 1528–1531. 10.1126/science.1091939. - DOI - PubMed
    1. Navarro Yerga R. M.; Álvarez Galván M. C.; del Valle F.; Villoria de la Mano J. A.; Fierro J. L. G. Water Splitting on Semiconductor Catalysts under Visible-Light Irradiation. ChemSusChem 2009, 2, 471–485. 10.1002/cssc.200900018. - DOI - PubMed
    1. Barton E. E.; Rampulla D. M.; Bocarsly A. B. Selective Solar-Driven Reduction of CO 2 to Methanol Using a Catalyzed p-GaP Based Photoelectrochemical Cell. J. Am. Chem. Soc. 2008, 130, 6342–6344. 10.1021/ja0776327. - DOI - PubMed

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