Photoredox matching of earth-abundant photosensitizers with hydrogen evolving catalysts by first-principles predictions
(2024) In Journal of Chemical Physics 160(7).- Abstract
Photoredox properties of several earth-abundant light-harvesting transition metal complexes in combination with cobalt-based proton reduction catalysts have been investigated computationally to assess the fundamental viability of different photocatalytic systems of current experimental interest. Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations using several GGA (BP86, BLYP), hybrid-GGA (B3LYP, B3LYP*), hybrid meta-GGA (M06, TPSSh), and range-separated hybrid (ωB97X, CAM-B3LYP) functionals were used to calculate relevant ground and excited state reduction potentials for photosensitizers, catalysts, and sacrificial electron donors. Linear energy correction factors for the DFT/TD-DFT results that provide the... (More)
Photoredox properties of several earth-abundant light-harvesting transition metal complexes in combination with cobalt-based proton reduction catalysts have been investigated computationally to assess the fundamental viability of different photocatalytic systems of current experimental interest. Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations using several GGA (BP86, BLYP), hybrid-GGA (B3LYP, B3LYP*), hybrid meta-GGA (M06, TPSSh), and range-separated hybrid (ωB97X, CAM-B3LYP) functionals were used to calculate relevant ground and excited state reduction potentials for photosensitizers, catalysts, and sacrificial electron donors. Linear energy correction factors for the DFT/TD-DFT results that provide the best agreement with available experimental reference results were determined in order to provide more accurate predictions. Among the selection of functionals, the B3LYP* and TPSSh sets of correction parameters were determined to give the best redox potentials and excited states energies, ΔEexc, with errors of ∼0.2 eV. Linear corrections for both reduction and oxidation processes significantly improve the predictions for all the redox pairs. In particular, for TPSSh and B3LYP*, the calculated errors decrease by more than 0.5 V against experimental values for catalyst reduction potentials, photosensitizer oxidation potentials, and electron donor oxidation potentials. Energy-corrected TPSSh results were finally used to predict the energetics of complete photocatalytic cycles for the light-driven activation of selected proton reduction cobalt catalysts. These predictions demonstrate the broader usefulness of the adopted approach to systematically predict full photocycle behavior for first-row transition metal photosensitizer-catalyst combinations more broadly.
(Less)
- author
- Losada, Iria Bolaño LU and Persson, Petter LU
- organization
- publishing date
- 2024-02
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Journal of Chemical Physics
- volume
- 160
- issue
- 7
- article number
- 074302
- publisher
- American Institute of Physics (AIP)
- external identifiers
-
- pmid:38375904
- scopus:85185626160
- ISSN
- 0021-9606
- DOI
- 10.1063/5.0174837
- language
- English
- LU publication?
- yes
- id
- 38eff8f8-4ac4-4031-9b0c-71a15b9dd2a0
- date added to LUP
- 2024-03-28 08:12:14
- date last changed
- 2025-10-26 01:11:05
@article{38eff8f8-4ac4-4031-9b0c-71a15b9dd2a0,
abstract = {{<p>Photoredox properties of several earth-abundant light-harvesting transition metal complexes in combination with cobalt-based proton reduction catalysts have been investigated computationally to assess the fundamental viability of different photocatalytic systems of current experimental interest. Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations using several GGA (BP86, BLYP), hybrid-GGA (B3LYP, B3LYP*), hybrid meta-GGA (M06, TPSSh), and range-separated hybrid (ωB97X, CAM-B3LYP) functionals were used to calculate relevant ground and excited state reduction potentials for photosensitizers, catalysts, and sacrificial electron donors. Linear energy correction factors for the DFT/TD-DFT results that provide the best agreement with available experimental reference results were determined in order to provide more accurate predictions. Among the selection of functionals, the B3LYP* and TPSSh sets of correction parameters were determined to give the best redox potentials and excited states energies, ΔE<sub>exc</sub>, with errors of ∼0.2 eV. Linear corrections for both reduction and oxidation processes significantly improve the predictions for all the redox pairs. In particular, for TPSSh and B3LYP*, the calculated errors decrease by more than 0.5 V against experimental values for catalyst reduction potentials, photosensitizer oxidation potentials, and electron donor oxidation potentials. Energy-corrected TPSSh results were finally used to predict the energetics of complete photocatalytic cycles for the light-driven activation of selected proton reduction cobalt catalysts. These predictions demonstrate the broader usefulness of the adopted approach to systematically predict full photocycle behavior for first-row transition metal photosensitizer-catalyst combinations more broadly.</p>}},
author = {{Losada, Iria Bolaño and Persson, Petter}},
issn = {{0021-9606}},
language = {{eng}},
number = {{7}},
publisher = {{American Institute of Physics (AIP)}},
series = {{Journal of Chemical Physics}},
title = {{Photoredox matching of earth-abundant photosensitizers with hydrogen evolving catalysts by first-principles predictions}},
url = {{http://dx.doi.org/10.1063/5.0174837}},
doi = {{10.1063/5.0174837}},
volume = {{160}},
year = {{2024}},
}