Quantum Chemical Studies of Light Harvesting

Curutchet, Carles; Mennucci, Benedetta

doi:10.1021/acs.chemrev.5b00700

Cited by 298 publications

(352 citation statements)

References 513 publications

(1,149 reference statements)

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“…In Table 1, we also compare electronic couplings estimated using eqn (2) with the reference data obtained by the FCD method. 6,7 As seen there is good agreement between the obtained and the FCD values.…”

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Direct estimation of the transfer integral for photoinduced electron transfer from TD DFT calculations

Blancafort

Voityuk

2017

Phys. Chem. Chem. Phys.

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The rate of photoinduced ET in molecular systems is controlled by electronic coupling of the locally excited and charge transfer states.We generalize the Bixon-Jortner-Verhoeven expression for electronic coupling to systems with a small energy gap and derive the transfer integral for charge separation in two model heterojunctions using the excitation energies and oscillator strengths computed with TD DFT. The estimated couplings are in good agreement with the reference values.Photoinduced electron transfer (ET) in biomolecules and organic heterojunctions is of increasing interest. often do not provide the transition dipole moment between excited states computed with the time-dependent density functional theory (TDDFT) method and therefore cannot be employed to obtain the coupling. There are also other issues that often prevent the use of standard calculations of the transfer integral (in most cases one needs a special computational code to obtain the coupling). In this paper, we consider a simple approach that allows one to estimate the coupling matrix element from routine QM calculations.In their landmark study, 20 Bixon, Jortner and Verhoeven derived the expressionwhich links the electronic coupling V of the LE and CT states with the experimental vertical excitation energies E LE and E CT and oscillator strengths f LE and f CT . Because the quantities E and f are always available from QM calculations of excited states, eqn (1) can also be used in combination with the QM methods.As noted explicitly by the authors, 20 eqn (1) is obtained on the condition that |V LE,CT /(E LE À E CT )| { 1, and thus cannot be applied to systems where the energy gap |E LE À E CT | and the coupling V LE , CT are of the same order of magnitude. In this paper, we derive a more general expressionwhich within the two-state model is applicable to any molecular system including systems with a small energy gap. To demonstrate the performance of this simple scheme, we consider photoinduced charge separation in two heterojunction structures closely related to that studied experimentally by Gelinas et al. + -A À is generated by irradiation decay due to ET from the donor to the acceptor. The electronic interaction (coupling) of these pure states j LE and j CT with energies e LE and e CT determines the probability of the ET reaction. It also mixes j LE and j CT leading to ''borrowing intensity'' by the adiabatic CT (for more details see ref. 1). To express electronic coupling via spectroscopic parameters, eqn (2), we use the orthogonal transformation of the adiabatic

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confidence: 70%

“…[1][2][3][4][5][6][7][8] . The ET rate is controlled by electronic coupling of the initial and final states.…”

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confidence: 99%

Direct estimation of the transfer integral for photoinduced electron transfer from TD DFT calculations

Blancafort

Voityuk

2017

Phys. Chem. Chem. Phys.

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“…[37][38][39] In photosynthesis, light absorption and efficient transport of the excitation energy is achieved by clusters of chromophores in proteins commonly called light harvesting complexes (LHCs). 2 Generally, the majority of chromophore pairs are sufficiently distant that their interaction is reasonably well described by expressions like (1). This has been shown to be true, for example, for most pairs in the well-studied FMO protein.…”

Section:   a B A Bmentioning

confidence: 94%

Importance and Nature of Short-Range Excitonic Interactions in Light Harvesting Complexes and Organic Semiconductors

Fornari

Rowe

Padula

et al. 2017

J. Chem. Theory Comput.

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Copies of full items can be used for personal research or study, educational, or not-for profit purposes without prior permission or charge. Provided that the authors, title and full bibliographic details are credited, a hyperlink and/or URL is given for the original metadata page and the content is not changed in any way. Publisher's statement:"This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Chemical Theory and Computation. copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work http://pubs.acs.org/page/policy/articlesonrequest/index.html ." A note on versions:The version presented here may differ from the published version or, version of record, if you wish to cite this item you are advised to consult the publisher's version. Please see the 'permanent WRAP URL above for details on accessing the published version and note that access may require a subscription. AbstractThe singlet excitonic coupling between many pairs of chromophores is evaluated in three different Light Harvesting Complexes (LHCs) and two organic semiconductors (amorphous and crystalline). This large database of structures is used to assess the relative importance of short-range (exchange, overlap, orbital) and long-range (Coulombic) excitonic coupling. We find that Mulliken atomic transition charges can introduce systematic errors in the Coulombic coupling and that the dipole-dipole interaction fails to capture the true Coulombic coupling even at intermolecular distances of up to 50 Å. The non-Coulombic short range contribution to the excitonic coupling is found to represent up to ~70% of the total value for molecules in close contact, while, as expected, it is found to be negligible for dimers not in close contact. For the face-to-face dimers considered here, the sign of the short range interaction is found to correlate with the sign of the Coulombic coupling, i.e. reinforcing it when it is already strong. We conclude that for molecules in van der Waals contact the inclusion of short range effects is essential for a quantitative description of the exciton dynamics.

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“…Light‐harvesting (LH) antennas are vital apparatuses for photosynthetic organisms to absorb sunlight and transfer the harvested energy to a charge‐separating system, known as a reaction center (RC) . LH antennas contain several pigments, including chlorophylls (Chls), bacteriochlorophylls (BChls), bilins, and carotenoids .…”

Section: Introductionmentioning

confidence: 99%

Self‐Assemblies of Zinc Bacteriochlorophyll‐d Analogues Having Amide, Ester, and Urea Groups as Substituents at 17‐Position and Observation of Lamellar Supramolecular Nanostructures

et al. 2018

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Chlorosomes are unique light-harvesting apparatuses in photosynthetic green bacteria. Single chlorosomes contain a large number of bacteriochlorophyll (BChl)-c, -d, -e, and -f molecules, which self-assemble without protein assistance. These BChl self-assemblies involving specific intermolecular interactions (Mg⋅⋅⋅O3 -H⋅⋅⋅O=C13 and π-π stacks of chlorin skeletons) in a chlorosome have been reported to be round-shaped rods (or tubes) with diameters of 5 or 10 nm, or lamellae with a layer spacing of approximately 2 nm. Herein, the self-assembly of synthetic zinc BChl-d analogues having ester, amide, and urea groups in the 17-substituent is reported. Spectroscopic analyses indicate that the zinc BChl-d analogues self-assemble in a nonpolar organic solvent in a similar manner to natural chlorosomal BChls with additional assistance by hydrogen-bonding of secondary amide (or urea) groups (CON-H⋅⋅⋅O=CNH). Microscopic analyses of the supramolecules of a zinc BChl-d analogue bearing amide and urea groups show round- or square-shaped rods with widths of about 65 nm. Cryogenic TEM shows a lamellar arrangement of the zinc chlorin with a layer spacing of 1.5 nm inside the rod. Similar thick rods are also visible in the micrographs of self-assemblies of zinc BChl-d analogues with one or two secondary amide moieties in the 17-substituent.

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Quantum Chemical Studies of Light Harvesting

Cited by 298 publications

References 513 publications

Direct estimation of the transfer integral for photoinduced electron transfer from TD DFT calculations

Direct estimation of the transfer integral for photoinduced electron transfer from TD DFT calculations

Importance and Nature of Short-Range Excitonic Interactions in Light Harvesting Complexes and Organic Semiconductors

Self‐Assemblies of Zinc Bacteriochlorophyll‐d Analogues Having Amide, Ester, and Urea Groups as Substituents at 17‐Position and Observation of Lamellar Supramolecular Nanostructures

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