Вот кого читать нужно Петрович, а не Шипова
www.chem.utoronto.ca/staff/SCHOLES/scholes_home.html
Quantum-coherence in energy transfer
Despite a century of study, researchers are still learning about basic physical chemistry by studying how the energy of absorbed light hops from one molecule to another. Our studies range from examining how proteins influence energy transfer at an atomic level of detail to the development of fundamental physical models that help us address questions basic to quantum-mechanics, quantum information science, and organic photovoltaics.
Natural light-harvesting antenna systems are a prominent component in the photosynthetic machinery. Numerous highly absorptive molecules, bound onto a protein scaffold, capture sunlight and funnel that energy to power reaction centers—specialized biological solar cells. While reaction center architecture is basically conserved across a multiplicity of photosynthetic species, light-harvesting antennae exhibit remarkable diversity as well as the ability to adapt to local light conditions and to regulate the operation of reaction centers. Researchers are learning that arrangements of the light-absorbing molecules are not random, but are carefully positioned to optimize flow of energy from the point where sunlight is absorbed to a reaction center. Typically, that energy funnel comprises ~200 molecules and energy is transferred, via a sequence of quantum mechanical energy transfer processes, distances of ~20–100 nm with near unit quantum efficiency. If researchers could learn how to move energy with such precision and efficiency over comparable distance, then enormous leaps in the development of cheap organic solar cell technology would ensue. This is a problem specific to organic photovoltaic research because excitation energy needs to be transferred to an interface before it can be dissociated into mobile carriers. Hence the active layer can only be as thick as the length scale over which excitation energy can be transferred during its nanosecond lifetime. That distance is known as the exciton diffusion length.
Recent discoveries in our group and at UC Berkeley suggest that light-harvesting in some photosynthetic proteins involves quantum-coherence. This has captured the attention of researches for several reasons. First, it means that quantum mechanical probability laws can prevail over the classical laws of kinetics, allowing the possibility that light-initiated processes can by controlled using the interference principles first described by Schrdinger, Dirac, Feynman, and others. Second, it raises the fascinating question: have these organisms developed quantum-mechanical strategies for light-harvesting to gain an evolutionary advantage?
References:
(a) Gregory D. Scholes “Quantum-coherent electronic energy transfer: Did Nature think of it first?” J. Phys. Chem. Lett. 1, 2–8 (2010). Invited Perspective for the first issue.
(b)Elisabetta Collini, Cathy Y. Wong, Krystyna E. Wilk, Paul M. G. Curmi, Paul Brumer, and Gregory D. Scholes, “Coherently wired light-harvesting in photosynthetic marine algae at ambient temperature” Nature Vol 463, 4 February 2010: doi:10.1038/nature08811.
(c) Elisabetta Collini Gregory D. Scholes, “Coherent dynamics in resonance energy transfer at room temperature: Quantum-mechanical energy migration along MEH-PPV chains” J. Phys. Chem. A, George Schatz Festschrift Special Issue 113, 4223–4241 (2009).
(d) Elisabetta Collini Gregory D. Scholes, “Quantum coherent energy migration in a conjugated polymer at room temperature” Science 323, 369-373 (2009).
(e) Silvia E. Braslavsky, Eduard Fron, Hernn B. Rodrguez, Enrique San Romn, Gregory D. Scholes, Gerd Schweitzer, Bernard Valeur, Jakob Wirz, “Pitfalls and limitations in the practical use of Frster’s theory of resonance energy transfer” Photochem. Photobiol. Sciences, Forum Article, Nicholas Tully Special Issue 7, 1444–1448 (2008).
Electronic Energy Transfer and Photosynthetic Light-Harvesting
1.Carles Curutchet, Aurora Muoz-Losa, Susanna Monti, Jacob Kongsted, Gregory D. Scholes and Benedetta Mennucci, “Electronic energy transfer in condensed phase studied by a polarizable QM/MM model” J. Chem. Theory and Computation 5, 1838–1848 (2009).
2.Elisabetta Collini Gregory D. Scholes, “Coherent dynamics in resonance energy transfer at room temperature: Quantum-mechanical energy migration along MEH-PPV chains” J. Phys. Chem. A, George Schatz Festschrift Special Issue 113, 4223–4241 (2009).
3.Tihana Mirkovic, Krystyna E. Wilk, Paul M. G. Curmi, Gregory D. Scholes, “Phycobiliprotein diffusion in chloroplasts of cryptophyte Rhodomonas CS24” Photosynth. Res. 100, 7–17 (2009).
4.Elisabetta Collini Gregory D. Scholes, “Quantum coherent energy migration in a conjugated polymer at room temperature” Science 323, 369–373 (2009).
5.Cathy Y. Wong, Carles Curutchet, Sergei Tretiak, Gregory D. Scholes, “Ideal dipole approximation fails to predict energy transfer and electronic coupling between semiconducting single-wall carbon nanotubes” J. Chem. Phys. (2009, accepted).
6.Silvia E. Braslavsky, Eduard Fron, Hernn B. Rodrguez, Enrique San Romn, Gregory D. Scholes, Gerd Schweitzer, Bernard Valeur, Jakob Wirz, “Pitfalls and limitations in the practical use of Frster’s theory of resonance energy transfer” Photochem. Photobiol. Sciences, Forum Article in Nicholas Tully Special Issue (2008).
7.Carles Curutchet, Alberto Franceschetti, Alex Zunger, Gregory D. Scholes, “Examining Frster Energy Transfer for Semiconductor Nanocrystalline Quantum Dot Donors and Acceptors” J. Phys. Chem. C Letter, ASAP Article; DOI: 10.1021/jp805682m (2008).
8.Yaser R. Khan, Tieneke E. Dykstra Gregory D. Scholes, “Exploring the Frster limit in a small FRET pair” Chem. Phys. Lett. 461, 305–309 (2008).
9.Carles Curutchet, Benedetta Mennucci, Gregory D. Scholes, David Beljonne, “Does Frster theory predict the rate of electronic energy transfer for a model dyad at low temperature?” J. Phys. Chem. B 112, 3759–3766 (2008).
10.Carles Curutchet, Gregory D. Scholes, Benedetta Mennucci and Roberto Cammi, “How Solvent Controls Electronic Energy Transfer and Light Harvesting: Towards a quantum mechanical description of reaction field and screening effects.” J. Phys. Chem. B 111, 13253–13265 (2007).
11.Tihana Mirkovic, Alexander B. Doust, Jeongho Kim, Krystyna E. Wilk, Carles Curutchet, Benedetta Mennucci, Roberto Cammi, Paul M. G. Curmib, and Gregory D. Scholes, “Ultrafast light harvesting dynamics in the cryptophyte phycocyanin 645” Photochem. Photobiol. Sciences, Special issue in honour of David Phillips 6, 964–975 (2007).
12.Gregory D. Scholes, Carles Curutchet, Benedetta Mennucci, Roberto Cammi Jacopo Tomasi, “How solvent controls electronic energy transfer and light harvesting” J. Phys. Chem. B Letter 111, 6978–6982 (2007).
13. Alexander B. Doust, Xiujuan Yang, Tieneke E. Dykstra, Kevin Koo Gregory D. Scholes, “Light-harvesting antennae for organic solar cells” Appl. Phys. Lett. 89, 213505 (3 pages) (2006).
14.C. D. De Wit, A. B. Doust, I. H. M. van Stokkum, J. P. Dekker, K. E. Wilk, P. M. G. Curmi, G. D. Scholes R. van Grondelle, “How energy funnels from the phycoerythrin antenna complex to photosystem I and photosytem II in cryptophyte Rhodomonas CS24 cells” J. Phys. Chem. B 110, 25066–25073 (2006).
15.Gregory D. Scholes and David L. Andrews, “Optical orientation of quantum dot spin states via resonance energy transfer,” Phys. Rev. B 72, 125331 (2005).
16.Alexander B. Doust, Delmar S. Larsen, Ivo H. M. van Stokkum, Krystyna E. Wilk, Paul M. G. Curmi, Rienk van Grondelle, and Gregory D. Scholes, “Mediation of ultrafast light-harvesting by a central dimer in phycoerythrin 545 studied by transient absorption,” J. Phys. Chem. B 109, 14219–14226 (2005).
17.E. Hennebicq, G. Pourtois, G. D. Scholes, L.M. Herz, D.M. Russell, C. Silva, S. Setayesh, K. Mllen, J. L. Brdas and D. Beljonne, “Exciton migration in rigid-rod conjugated polymers: An improved Frster model,” J. Am. Chem. Soc. 127, 4744-4762 (2005).
18.H. Wiesenhofer, D. Beljonne, G.D. Scholes, E. Hennebicq, J.L. Brdas, and E. Zojer, “Limitations
of the Frster Description of Singlet Exciton Migration: The illustrative Example of transfer to Ketonic Defects in ladder-type Poly(para-phenylenes),” Adv. Functional Mater. 15, 155-160 (2005).
19.Alexander B. Doust, Christopher N. J. Marai, Stephen J. Harrop, Krystyna E. Wilk, Paul M.G. Curmi Gregory D. Scholes, “Developing a Structure - Function Model for the Cryptophyte Phycoerythrin 545 using ultrahigh resolution crystallography and ultrafast laser spectroscopy,” J. Mol. Biol. 344, 135-153 (2004).
20.Christopher N. J. Marai, Gregory A. Chass, Alexander B. Doust, Gregory D. Scholes, “An ab initio conformational study on 2,3-dihydrobilin-1,19(21H,24H)-dione, a model compound for open-chain tetrapyrroles,” J. Mol. Structure Theochem 680, 219-225 (2004).
21.X. J. Jordanides, G. D. Scholes, W. A. Shapley, J. R. Reimers, G. R. Fleming, “Electronic couplings and energy transfer dynamics in the oxidized primary electron donor of the bacterial reaction center,” J. Phys. Chem. B. 108, 1753-1765 (2004).
22.D. Beljonne, G. Pourtois, Z. Shuai, E. Hennebicq, G.D. Scholes, J.-L. Bredas, “Energy transfer in p-conjugated polymers: Interchain vs. intrachain processes in polyindenofluorence,” Synth. Metals 137, 1369-1371 (2003).
23.J. M. Salverda, M. Vengris, B. P. Krueger, G. D. Scholes, A. R. Czarnoleski, V. Novoderezhkin, H. van Amerongen, and R. van Grondelle, “Energy transfer in light-harvesting complexes LHC-II and CP29 of spinach studied with three-pulse echo peak shift and transient grating,” Biophys. J. 84, 450-465 (2003).
24.D. Beljonne, G. Pourtois, C. Silva, E. Hennebicq, D.M. Russell, R.H. Friend, G.D. Scholes, S. Setayesh, S. Becker, D. Marsitsky, K. Mllen, J.L. Brdas, “Interchain vs. intrachain energy transfer in a perylene end-capped polyindenofluorene,” Proc. Natl. Acad. Sci. USA 99, 10982-10987 (2002).
25.Gregory D. Scholes, “Designing light-harvesting antenna systems based on superradiant molecular aggregates,” Chem. Phys. 275, 373-386 (2002).
26.Gregory D. Scholes, Xanthipe J. Jordanides, and Graham R. Fleming, “Adapting the Frster theory of energy transfer for modeling dynamics in aggregated molecular assemblies,” J. Phys. Chem. B 105, 1640-1651 (2001).
27.Xanthipe J. Jordanides, Gregory D. Scholes, and Graham R. Fleming. “The mechanism of energy transfer in the photosynthetic reaction center,” J. Phys. Chem. B 105, 1652-1669 (2001).
28.Peter J. Walla, Patricia A. Linden, Gregory D. Scholes Graham R. Fleming, “Fs-dynamics of the forbidden carotenoid S? state in light-harvesting complexes of purple bacteria observed after two-photon excitation,” Proc. Natl. Acad. Science USA 97, 10808-10813 (2000).
29.Gregory D. Scholes and Graham R. Fleming, “On the mechanism of light-harvesting in photosynthetic purple bacteria: B800 to B850 energy transfer,” J. Phys. Chem. B, 104, 1854-1868 (2000).
30.Ritesh Agarwal, Brent P. Krueger, Gregory D. Scholes, Mino Yang, Jenny Yom, Laurens Mets Graham R. Fleming, “Ultrafast energy transfer in LHC-II revealed by three-pulse echo peak shift measurements,” J. Phys. Chem. B. 104, 2908-2918 (2000).
31.Brent P. Krueger, Gregory D. Scholes, Ian R, Gould, Graham R. Fleming, “Carotenoid mediated B800-B850 coupling in LH2,” Phys. Chem. Comm. 8 (1999).
32.G. D. Scholes, Ian R, Gould, Richard J. Cogdell, Graham R. Fleming, “Ab initio molecular orbital calculations of electronic couplings in the LH2 bacterial light-harvesting complex of Rps. acidophilia,” J. Phys. Chem. B. 103, 2453-2553 (1999).
33.Brent. P. Krueger, Gregory D. Scholes, and Graham R. Fleming, “Calculation of couplings and energy transfer pathways between the pigments of LH2 by the ab initio transition density cube method,” J. Phys. Chem B 102, 5378-5386, (1998).
34.Brent P. Krueger, Gregory D. Scholes, Ralph Jimenez, Graham R. Fleming, “Electronic excitation energy transfer from carotenoid to bacteriochlorophyll in the purple bacterium Rhodopseudomonas acidophilia,” J. Phys. Chem. B. 102, 2284-2292, (1998).
35.R. D. Harcourt, K. P. Ghiggino, G. D. Scholes, R. P. Steer, “Matrix element for electronic energy transfer: S?S? S?S? excited state annihilation,” J. Chem. Phys. 109, 1310-1314 (1998).
36.Gregory D. Scholes and David L. Andrews, “Damping and Higher Multipole Effects in the Quantum Electrodynamical Model for Electronic Energy Transfer in the Condensed Phase,” J. Chem. Phys. 107 5374-5384 (1997).
37.Gregory D. Scholes, Richard D. Harcourt, Graham R. Fleming, “Electronic Interactions in Photosynthetic Light-Harvesting Complexes: The Role of Carotenoids,” J. Phys. Chem. B 101, 7302-7312 (1997).
38.Gregory D. Scholes, “Energy Transfer and Spectroscopic Characterization of Multichromophoric Assemblies,” J. Phys. Chem. 100, 18731-18739 (1996).
39.Richard D. Harcourt, Kenneth P. Ghiggino, Gregory D. Scholes, Shammi Speiser, “On the Origin of Matrix Elements for Electronic Excitation (Energy) Transfer,” J. Chem. Phys. 105, 1897-1901 (1996).
40.Gregory D. Scholes and Richard D. Harcourt, “Configuration Interaction and the Theory of Columbic Interactions in Energy Transfer and Molecular Exciton Interactions,” J. Chem. Phys. 104, 5054-5061 (1996).
41.Gregory D. Scholes and Kenneth P. Ghiggino, “Rate Expressions for Excitation Transfer IV. Energy Migration and Superexchange Phenomena,” J. Chem. Phys. 103, 8873-8883 (1995).
42.Gregory D. Scholes, Richard D. Harcourt, and Kenneth P. Ghiggino, “Rate Expressions for Excitation Transfer: III, An ab initio study of Electronic Factors in Excitation Transfer and Exciton Resonance Interactions,” J. Chem. Phys. 102, 9574-9581 (1995).
43.Richard D. Harcourt, Gregory D. Scholes and Kenneth P. Ghiggino, “Rate Expressions for Excitation Transfer: II. Electronic Considerations of Direct and Through-Configuration Exciton Resonance Interactions,” J. Chem Phys. 101, 10521-10525 (1994).
44.Gregory D. Scholes and Kenneth P. Ghiggino, “Rate Expressions for Excitation Transfer: I. Radiationless Transition Theory Perspective,” J. Chem Phys. 1251-1261 (1994).
45.Gregory D. Scholes and Kenneth Ghiggino, “Mechanisms of Excitation Transfer in Multichromophoric Systems,” J. Photochem. Photobiol. A: Chem. 80, 355-362 (1994).
46.Gregory D. Scholes and Kenneth P. Ghiggino, “Electronic Interactions and Interchromophore Excitation Transfer,” J. Phys. Chem. 98, 4580-4590 (1994).
47.Gregory D. Scholes, Kenneth P. Ghiggino, Anna M. Oliver, Michael N. Paddon-Row, “Intramolecular Electronic Energy Transfer Between Rigidly Linked Naphthalene and Anthracene Chromophores,” J. Phys. Chem. 97, 11871 (1993).
48.Gregory D. Scholes, Andrew H. A. Clayton, Kenneth P. Ghiggino, “On the Rate of Radiationless Intermolecular Energy Transfer,” J. Chem. Phys. 97, 7405 (1992).
Отредактировано limarukraine (2010-04-25 16:40:36)
