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Plasmon-controlled Light-harvesting

Presented at the Avogadro Colloquium 2013, Scuola Normale Superiore of Pisa, Italy
by

Oliviero Andreussi

on 28 November 2013

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Transcript of Plasmon-controlled Light-harvesting

Plasmon-Controlled Light-Harvesting:
Design Rules for
Bio-Hybrid Devices
via
Multiscale Modeling

Department of Chemistry
University of Pisa
PCM
Polarizable Continuum Model
METAL
EET
Excitation Energy Transfer
MMPol
Classical Polarizable Force-Field
Miertus, Scrocco and Tomasi, Chem. Phys. 1981, 55, 117
Tomasi and Persico, Chem. Rev. 1994, 94, 2027
Tomasi, Mennucci and Cammi, Chem. Rev. 2005, 105(8), 2999
LH Proteins
S. Corni, J. Tomasi J. Chem. Phys. 114, 3739 (2001).

Multiscale Model
Bio-Hybrid devices
Image by Oliviero Andreussi
Image by Stefano Caprasecca
Image by Oliviero Andreussi
Experiments
Silver-Islands Film + PCP LH Protein
Makowski et al. Nano Lett. 2008, 8, 558
8 Peridinins
(PIDs)

+ 2 Chlorophylls
(CHL)
Single molecule spectroscopy (EET process):
- average 6-fold enhancement
- maximum 18-fold enhancement

Ensemble molecule spectroscopy:
- average 6-fold enhancement for EET process
- average 8.5-fold enhancement for direct process
Direct Process: CHL absorption and emission
EET Process: PIDs absorption CHL emission
Results
Orientation Effects
Direct Process
EET Process
R = 30 nm
Sphere (S)
Triple (T)
Double (D)
Simulations
O. Andreussi, A. Biancardi, S. Corni and B. Mennucci Nano Lett. 2013, 13, 4475
Direct Process
EET-mediated Process
Single Sphere: Orientation Effects
Conclusions
Main features of our approach:
- excitonic description of PIDs
absorption
- realistic EET couplings, beyond the
dipole approximation
- full control on metal shape and
system setup
Main approximations:
- S1-S2 states of carotenoids
- crystal structure geometries
- simplified kinetic model
On going:
- classical MD to sample equilibrium
configurations
- benchmarking of DFT functional with
MRCI to improve S1 states
- realistic time evolution of excitation
energy
QM: semiempirical ZINDO calculations, benchmarked against DFT

MMPol: ab-initio based (RESP) atomic charges, Thole atomic polarizabilities

PCM: only the metal interface, experimental Ag optical permittivity from Palik
Computational Details
Chromophores bundles

- absorb the highest fraction of solar light
- funnel the energy towards the reaction centers
- work in very low intensity conditions
- photo-protect the protein and the cell
Plasmonic properties of the system
Radiative Decay Rate
Non-radiative Decay Rate
Absorption Coefficient
2001
M.F. Iozzi, B. Mennucci, J. Tomasi, R. Cammi, J. Chem. Phys. 120 7029 (2004)
EET Rates
C. Curutchet et al. J. Chem. Theory Comput. 51838 (2009)
2009
2004
O. Andreussi,
A. Biancardi, S. Corni and B. Mennucci
Complex heterogeneous environments
fully polarizable
Full transcript