1. Principles of charge separator design for artificial photosynthesis
0 | 14
Principles of charge separator design for
artificial photosynthesis
Thomas J. Eisenmayer
Universiteit Leiden
Leiden Institute of Chemistry.

2. Principles of charge separator design for artificial photosynthesis
Introduction 1 | 14
100% quantum
efficiency
Leiden Institute of Chemistry.

3. Principles of charge separator design for artificial photosynthesis
Introduction 1 | 14
Leiden Institute of Chemistry.

4. Principles of charge separator design for artificial photosynthesis
Anisotropic electron transfer 2 | 14
Leiden Institute of Chemistry.

5. Principles of charge separator design for artificial photosynthesis
Anisotropic electron transfer 2 | 14
• Coupled to well-defined
vibrational coherences
Leiden Institute of Chemistry.

6. Principles of charge separator design for artificial photosynthesis
Model and methods 3 | 14
The Special Pair
AIMD
d 2 Ri
Mi =− i Ψ0 | He |Ψ0
dt 2
He Ψ0 = E0 Ψ0
ROKS
E (S1 ) = 2E (m) − E (t)
Leiden Institute of Chemistry.

7. Principles of charge separator design for artificial photosynthesis
Frontier orbital localization 4 | 14
• HOMO • LUMO
+ − − +
|PL PM |P ∗ |PL PM
Leiden Institute of Chemistry.

8. Principles of charge separator design for artificial photosynthesis
Frontier orbital localization 4 | 14
• HOMO • LUMO
+ − − +
|PL PM |P ∗ |PL PM
Leiden Institute of Chemistry.

9. Principles of charge separator design for artificial photosynthesis
Frontier orbital localization 4 | 14
• HOMO • LUMO
+ − − +
|PL PM |P ∗ |PL PM
Leiden Institute of Chemistry.

10. Principles of charge separator design for artificial photosynthesis
Frontier orbital localization 4 | 14
• HOMO • LUMO
+ − − +
|PL PM |P ∗ |PL PM
Leiden Institute of Chemistry.

11. Principles of charge separator design for artificial photosynthesis
Low-frequency vibrational modes 5 | 14
Leiden Institute of Chemistry.

12. Principles of charge separator design for artificial photosynthesis
Anisotropic charge displacement 6 | 14
T.J. Eisenmayer et al., J. Phys. Chem. Lett, 2012, 3 (6), pp 694-697
Leiden Institute of Chemistry.

13. Principles of charge separator design for artificial photosynthesis
Weakening of a hydrogen bond 7 | 14
...prevents the back-reaction
Leiden Institute of Chemistry.

14. Principles of charge separator design for artificial photosynthesis
Model and methods 8 | 14
Including the acceptor
CDFT
w(r )ρ(r )d (r ) − Nc = 0
AIMD
d 2 Ri
Mi =− i Ψ0 | He |Ψ0
dt 2
He Ψ0 = E0 Ψ0
Leiden Institute of Chemistry.

15. Principles of charge separator design for artificial photosynthesis
Water A as a ± 32 cm−1 switch 9 | 14
Leiden Institute of Chemistry.

16. Principles of charge separator design for artificial photosynthesis
Increased coupling 10 | 14
• The donor-acceptor electronic coupling increases with 35% along
the suggested reaction coordinate
Leiden Institute of Chemistry.

17. Principles of charge separator design for artificial photosynthesis
Conclusion 11 | 14
• Removing the barrier
→ HisM202 rotation
• Facilitating electron transfer
→ Collinear proton
displacement
• Preventing the back-reaction
→ Orthogonal proton
displacement
T.J. Eisenmayer, J. Lasave, F. Buda, to be submitted
Leiden Institute of Chemistry.

18. Principles of charge separator design for artificial photosynthesis
Why is the PSII oxidation potential so high? 12 | 14
• the HOMO-5 (PD1 ) is • the dielectric constant is low
localized ≈2
Leiden Institute of Chemistry.

19. Principles of charge separator design for artificial photosynthesis
Towards artificial photosynthesis 13 | 14
Leiden Institute of Chemistry.

20. Principles of charge separator design for artificial photosynthesis
Donor-acceptor complex 14 | 14
future direction: develop a method to calculate the quantum yield for systems of 50-100 atoms.
Leiden Institute of Chemistry.

21. Principles of charge separator design for artificial photosynthesis
Donor-acceptor complex 14 | 14
future direction: develop a method to calculate the quantum yield for systems of 50-100 atoms.
Leiden Institute of Chemistry.

22. Principles of charge separator design for artificial photosynthesis
Donor-acceptor complex 14 | 14
future direction: develop a method to calculate the quantum yield for systems of 50-100 atoms.
Leiden Institute of Chemistry.

23. Principles of charge separator design for artificial photosynthesis
Donor-acceptor complex 14 | 14
future direction: develop a method to calculate the quantum yield for systems of 50-100 atoms.
Leiden Institute of Chemistry.

24. Principles of charge separator design for artificial photosynthesis
Acknowledgements 14 | 14
• Francesco Buda • Jeroen Rombouts (VU)
• Huub J.M. de Groot • Adriano Monti
• Johannes Neugebauer • Elbert van de Wetering
(TU Braunschweig) • Huub Adriaanse
• Jorge Lasave (Conicet) • Nitin Bughwansing
Leiden Institute of Chemistry.