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Photosynthetic reaction center as a quantum heat engine.

ABSTRACT: Two seemingly unrelated effects attributed to quantum coherence have been reported recently in natural and artificial light-harvesting systems. First, an enhanced solar cell efficiency was predicted and second, population oscillations were measured in photosynthetic antennae excited by sequences of coherent ultrashort laser pulses. Because both systems operate as quantum heat engines (QHEs) that convert the solar photon energy to useful work (electric currents or chemical energy, respectively), the question arises whether coherence could also enhance the photosynthetic yield. Here, we show that both effects arise from the same population-coherence coupling term which is induced by noise, does not require coherent light, and will therefore work for incoherent excitation under natural conditions of solar excitation. Charge separation in light-harvesting complexes occurs in a pair of tightly coupled chlorophylls (the special pair) at the heart of photosynthetic reaction centers of both plants and bacteria. We show the analogy between the energy level schemes of the special pair and of the laser/photocell QHEs, and that both population oscillations and enhanced yield have a common origin and are expected to coexist for typical parameters. We predict an enhanced yield of 27% in a QHE motivated by the reaction center. This suggests nature-mimicking architectures for artificial solar energy devices.

SUBMITTER: Dorfman KE

PROVIDER: S-EPMC3581952 | biostudies-literature | 2013 Feb

REPOSITORIES: biostudies-literature

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Photosynthetic reaction center as a quantum heat engine.

Dorfman Konstantin E KE Voronine Dmitri V DV Mukamel Shaul S Scully Marlan O MO

Proceedings of the National Academy of Sciences of the United States of America 20130130 8

Two seemingly unrelated effects attributed to quantum coherence have been reported recently in natural and artificial light-harvesting systems. First, an enhanced solar cell efficiency was predicted and second, population oscillations were measured in photosynthetic antennae excited by sequences of coherent ultrashort laser pulses. Because both systems operate as quantum heat engines (QHEs) that convert the solar photon energy to useful work (electric currents or chemical energy, respectively), ...[more]

PMID: 23365138

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Project description:Laser and photocell quantum heat engines (QHEs) are powered by thermal light and governed by the laws of quantum thermodynamics. To appreciate the deep connection between quantum mechanics and thermodynamics we need only recall that in 1901 Planck introduced the quantum of action to calculate the entropy of thermal light, and in 1905 Einstein's studies of the entropy of thermal light led him to introduce the photon. Then in 1917, he discovered stimulated emission by using detailed balance arguments. Half a century later, Scovil and Schulz-DuBois applied detailed balance ideas to show that maser photons were produced with Carnot quantum efficiency (see Fig. 1A). Furthermore, Shockley and Quiesser invoked detailed balance to obtain the efficiency of a photocell illuminated by "hot" thermal light (see Fig. 2A). To understand this detailed balance limit, we note that in the QHE, the incident light excites electrons, which can then deliver useful work to a load. However, the efficiency is limited by radiative recombination in which the excited electrons are returned to the ground state. But it has been proven that radiatively induced quantum coherence can break detailed balance and yield lasing without inversion. Here we show that noise-induced coherence enables us to break detailed balance and get more power out of a laser or photocell QHE. Surprisingly, this coherence can be induced by the same noisy (thermal) emission and absorption processes that drive the QHE (see Fig. 3A). Furthermore, this noise-induced coherence can be robust against environmental decoherence.Fig. 1.(A) Schematic of a laser pumped by hot photons at temperature T(h) (energy source, blue) and by cold photons at temperature T(c) (entropy sink, red). The laser emits photons (green) such that at threshold the laser photon energy and pump photon energy is related by Carnot efficiency (4). (B) Schematic of atoms inside the cavity. Lower level b is coupled to the excited states a and ?. The laser power is governed by the average number of hot and cold thermal photons, and . (C) Same as B but lower b level is replaced by two states b(1) and b(2), which can double the power when there is coherence between the levels.Fig. 2.(A) Schematic of a photocell consisting of quantum dots sandwiched between p and n doped semiconductors. Open circuit voltage and solar photon energy ??(h) are related by the Carnot efficiency factor where T(c) is the ambient and T(h) is the solar temperature. (B) Schematic of a quantum dot solar cell in which state b is coupled to a via, e.g., solar radiation and coupled to the valence band reservoir state ? via optical phonons. The electrons in conduction band reservoir state ? pass to state ? via an external circuit, which contains the load. (C) Same as B but lower level b is replaced by two states b(1) and b(2), and when coherently prepared can double the output power.Fig. 3.(A) Photocell current j = ??(??) (laser photon flux P(l)/?(?(l))) (in arbitrary units) generated by the photovoltaic cell QHE (laser QHE) of Fig. 1C (Fig. 2C) as a function of maximum work (in electron volts) done by electron (laser photon) E(?) - E(?) + kT(c) log(?(??)/?(??)) with full (red line), partial (brown line), and no quantum interference (blue line). (B) Power of a photocell of Fig. 2C as a function of voltage for different decoherence rates , 100?(1c). Upper curve indicates power acquired from the sun.

Project description:Photosynthetic reaction centers convert excitation energy from absorbed sunlight into chemical potential energy in the form of a charge-separated state. The rates of the electron transfer reactions necessary to achieve long-lived, high-energy charge-separated states with high quantum yields are determined in part by precise control of the electronic coupling among the chromophores, donors, and acceptors and of the reaction energetics. Successful artificial photosynthetic reaction centers for solar energy conversion have similar requirements. Control of electronic coupling in particular necessitates chemical linkages between active component moieties that both mediate coupling and restrict conformational mobility so that only spatial arrangements that promote favorable coupling are populated. Toward this end, we report the synthesis, structure, and photochemical properties of an artificial reaction center containing two porphyrin electron donor moieties and a fullerene electron acceptor in a macrocyclic arrangement involving a ring of 42 atoms. The two porphyrins are closely spaced, in an arrangement reminiscent of that of the special pair in bacterial reaction centers. The molecule is produced by an unusual cyclization reaction that yields mainly a product with C(2) symmetry and trans-2 disubstitution at the fullerene. The macrocycle maintains a rigid, highly constrained structure that was determined by UV-vis spectroscopy, NMR, mass spectrometry, and molecular modeling at the semiempirical PM6 and DFT (B3LYP/6-31G**) levels. Transient absorption results for the macrocycle in 2-methyltetrahydrofuran reveal photoinduced electron transfer from the porphyrin first excited singlet state to the fullerene to form a P(•+)-C(60)(•-)-P charge separated state with a time constant of 1.1 ps. Photoinduced electron transfer to the fullerene excited singlet state to form the same charge-separated state has a time constant of 15 ps. The charge-separated state is formed with a quantum yield of essentially unity and has a lifetime of 2.7 ns. The ultrafast charge separation coupled with charge recombination that is over 2000 times slower is consistent with a very rigid molecular structure having a small reorganization energy for electron transfer, relative to related porphyrin-fullerene molecules.

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Photosynthetic reaction center as a quantum heat engine.

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Photosynthetic reaction center as a quantum heat engine.

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