Automated assessment of redox potentials for dyes in dye-sensitized photoelectrochemical cells

Belić, Jelena; Förster, A.; Menzel, Jan Paul; Buda, Francesco; Visscher, Lucas

doi:10.1039/d1cp04218a

Cited by 6 publications

(6 citation statements)

References 94 publications

(107 reference statements)

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“…If not stated otherwise, in all qs GW calculations, we first perform a PBE0 calculation with 40% exact exchange (PBEH40), which is a good preconditioner for qs GW and leads to fast convergence. 157 Aside from numerical inaccuracies, the final results are independent of this choice, which we have verified in ref ( 133 ) and which we will verify also for the case of Chla in the next section. For qs GW , we terminate the calculations when the Frobenius norm of the difference between the density matrices of two subsequent iterations falls below 5 × 10 –9 .…”

Section: Computational Detailssupporting

confidence: 60%

“…Also, in all KS calculations, we set the threshold for the Löwdin orthogonalization to 5 × 10 –3 . If not stated otherwise, in all qs GW calculations, we first perform a PBE0 calculation with 40% exact exchange (PBEH40), which is a good preconditioner for qs GW and leads to fast convergence . Aside from numerical inaccuracies, the final results are independent of this choice, which we have verified in ref and which we will verify also for the case of Chla in the next section.…”

Section: Computational Detailsmentioning

confidence: 96%

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Quasiparticle Self-Consistent GW-Bethe–Salpeter Equation Calculations for Large Chromophoric Systems

Förster

Visscher

2022

J. Chem. Theory Comput.

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The GW-Bethe−Salpeter equation (BSE) method is promising for calculating the low-lying excitonic states of molecular systems. However, so far it has only been applied to rather small molecules and in the commonly implemented diagonal approximations to the electronic self-energy, it depends on a mean-field starting point. We describe here an implementation of the self-consistent and starting-point-independent quasiparticle self-consistent (qsGW)-BSE approach, which is suitable for calculations on large molecules. We herein show that eigenvalue-only self-consistency can lead to an unfaithful description of some excitonic states for chlorophyll dimers while the qsGW-BSE vertical excitation energies (VEEs) are in excellent agreement with spectroscopic experiments for chlorophyll monomers and dimers measured in the gas phase. Furthermore, VEEs from time-dependent density functional theory calculations tend to disagree with experimental values and using different range-separated hybrid (RSH) kernels does change the VEEs by up to 0.5 eV. We use the new qsGW-BSE implementation to calculate the lowest excitation energies of the six chromophores of the photosystem II (PSII) reaction center (RC) with nearly 2000 correlated electrons. Using more than 11,000 (6000) basis functions, the calculation could be completed in less than 5 (2) days on a single modern compute node. In agreement with previous TD-DFT calculations using RSH kernels on models that also do not include environmental effects, our qsGW-BSE calculations only yield states with local characters in the low-energy spectrum of the hexameric complex. Earlier works with RSH kernels have demonstrated that the protein environment facilitates the experimentally observed interchromophoric charge transfer. Therefore, future research will need to combine correlation effects beyond TD-DFT with an explicit treatment of environmental electrostatics.

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Section: Computational Detailssupporting

confidence: 60%

Section: Computational Detailsmentioning

confidence: 96%

Quasiparticle Self-Consistent GW-Bethe–Salpeter Equation Calculations for Large Chromophoric Systems

Förster

Visscher

2022

J. Chem. Theory Comput.

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“…As shown in the blue path of Figure , the direct method calculates the Gibbs free energy difference between the ion and neutral states in solution Eqs and can be used to calculate the redox potential of anions and cations by the direct method E normalr normale normald ( normalC + ) = prefix− G normals normalo normall ( C ) − G normals normalo normall ( normalC + ) n F − 1.44 E normalo normalx ( normalA − ) = G normals normalo normall ( A ) − G normals normalo normall ( normalA − ) n F − 1.44 It should be noted that when the calculation conditions used by the thermodynamic direct method and cycle method are identical (with the same solvation model and theoretical level), the free energy results obtained by both methods are exactly the same.…”

Section: Calculation Methodsmentioning

confidence: 99%

“…As shown in the blue path of Figure 4, the direct method calculates the Gibbs free energy difference between the ion and neutral states in solution. 23 Eqs 14 and 15 can be used to calculate the redox potential of anions and cations by the direct method…”

Section: Thermodynamic Direct Methodmentioning

confidence: 99%

Strategies to Improve the Quantum Computation Accuracy for Electrochemical Windows of Ionic Liquids

Wang,

Wang

2024

J. Phys. Chem. B

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Rational design of ionic liquids (ILs) with wide electrochemical windows (ECWs) for high-voltage cathodes is essential to elevating the energy density of current rechargeable batteries. It is significant to determine appropriate strategies for accurately predicting the ECWs of ILs. In this study, we compare the calculated ECWs based on three quantum methods, including the highest occupied molecular orbital−lowest unoccupied molecular orbital (HOMO−LUMO) method, the ionization potential−electron affinity (IP−EA) method, and the thermodynamic method, under four unique combinations of simulation environments, and assess the discrepancies between the calculated and the experimental results of ECWs. For the three quantum methods, although HOMO−LUMO and IP−EA methods show limited prediction accuracy compared to the experimental values, they can qualitatively rank the anodic limits of anions and the cathodic limits of cations. For the thermodynamic method, we demonstrate that the highest accuracy can be achieved by considering the most rational redox reaction process. By varying the calculation environments, the calculated ECWs tend to be underestimated by considering separate cations and anions of ILs under gas phase, whereas they always exhibit overestimated results when calculating based on the cation−anion pairs. When the computation considers isolated ions with the solvent model plus proper thermodynamic corrections, we observe improved consistency with the experimental results. Though all methods have limitations to achieving perfect predictions of ECWs, we believe rational selection of calculation methods based on application-oriented scenarios can balance the efficiency and accuracy of the results for the development of a high-throughput and accurate database of ECWs for ILs.

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“…36 To calculate the ground-state oxidation potential (GSOP) of the dyes, we consider the negative of the highest occupied molecular orbital (HOMO) energy of the neutral molecule in THF using the CPCM framework, while the excited-state oxidation potential (ESOP) was calculated from the summation of the GSOP and the first excited state from the TD-DFT calculation corresponding to the band gap of the dye. 37…”

Section: Methodsmentioning

confidence: 99%

Effect of π-Spacer Length in Novel Xanthene-Linked l-(D−π–A)₂-Type Dianchoring Dyes for Dye-Sensitized Solar Cells

Baptayev

Kim

Bolatbek

et al. 2022

ACS Appl. Energy Mater.

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The effect of thiophene π-spacer length was studied in xanthene-linked l-(D−π–A)2-type dianchoring dye performance in dye-sensitized solar cells. The photophysical, electrochemical, and photovoltaic performances of KS-19 with single thiophene and KS-21 with dithiophene units as π-spacers were compared. The overall result showed that the presence of an extra thiophene unit in KS-21 led to the extension of conjugation, causing broadening and a red-shift of light absorption which in turn resulted in increased J SC and power conversion efficiency (PCE).

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Automated assessment of redox potentials for dyes in dye-sensitized photoelectrochemical cells

Abstract: Sustainable solutions for hydrogen production, such as dye-sensitized photoelectrochemical cells (DS-PEC), rely on the fundamental properties of its components whose modularity allows for their separate investigation. In this work, we...

Cited by 6 publications

References 94 publications

Quasiparticle Self-Consistent GW-Bethe–Salpeter Equation Calculations for Large Chromophoric Systems

Quasiparticle Self-Consistent GW-Bethe–Salpeter Equation Calculations for Large Chromophoric Systems

Strategies to Improve the Quantum Computation Accuracy for Electrochemical Windows of Ionic Liquids

Effect of π-Spacer Length in Novel Xanthene-Linked l-(D−π–A)₂-Type Dianchoring Dyes for Dye-Sensitized Solar Cells

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Automated assessment of redox potentials for dyes in dye-sensitized photoelectrochemical cells

Abstract: Sustainable solutions for hydrogen production, such as dye-sensitized photoelectrochemical cells (DS-PEC), rely on the fundamental properties of its components whose modularity allows for their separate investigation. In this work, we...

Cited by 6 publications

References 94 publications

Quasiparticle Self-Consistent GW-Bethe–Salpeter Equation Calculations for Large Chromophoric Systems

Quasiparticle Self-Consistent GW-Bethe–Salpeter Equation Calculations for Large Chromophoric Systems

Strategies to Improve the Quantum Computation Accuracy for Electrochemical Windows of Ionic Liquids

Effect of π-Spacer Length in Novel Xanthene-Linked l-(D−π–A)2-Type Dianchoring Dyes for Dye-Sensitized Solar Cells

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Effect of π-Spacer Length in Novel Xanthene-Linked l-(D−π–A)₂-Type Dianchoring Dyes for Dye-Sensitized Solar Cells