| 1. |
- Cao, J. S., et al.
(författare)
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Quantum biology revisited
- 2020
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Ingår i: Science Advances. - : American Association for the Advancement of Science (AAAS). - 2375-2548. ; 6:14
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Tidskriftsartikel (refereegranskat)abstract
- Photosynthesis is a highly optimized process from which valuable lessons can be learned about the operating principles in nature. Its primary steps involve energy transport operating near theoretical quantum limits in efficiency. Recently, extensive research was motivated by the hypothesis that nature used quantum coherences to direct energy transfer. This body of work, a cornerstone for the field of quantum biology, rests on the interpretation of small-amplitude oscillations in two-dimensional electronic spectra of photosynthetic complexes. This Review discusses recent work reexamining these claims and demonstrates that interexciton coherences are too short lived to have any functional significance in photosynthetic energy transfer. Instead, the observed long-lived coherences originate from impulsively excited vibrations, generally observed in femtosecond spectroscopy. These efforts, collectively, lead to a more detailed understanding of the quantum aspects of dissipation. Nature, rather than trying to avoid dissipation, exploits it via engineering of exciton-bath interaction to create efficient energy flow.
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| 2. |
- Chábera, Pavel, et al.
(författare)
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A low-spin Fe(iii) complex with 100-ps ligand-to-metal charge transfer photoluminescence
- 2017
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Ingår i: Nature. - : Springer Science and Business Media LLC. - 0028-0836 .- 1476-4687. ; 543:7647, s. 695-699
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Tidskriftsartikel (refereegranskat)abstract
- Transition-metal complexes are used as photosensitizers1, in light-emitting diodes, for biosensing and in photocatalysis2. A key feature in these applications is excitation from the ground state to a charge-transfer state3,4; the long charge-transfer-state lifetimes typical for complexes of ruthenium5 and other precious metals are often essential to ensure high performance. There is much interest in replacing these scarce elements with Earth-abundant metals, with iron6 and copper7 being particularly attractive owing to their low cost and non-toxicity. But despite the exploration of innovative molecular designs6,8,9,10, it remains a formidable scientific challenge11 to access Earth-abundant transition-metal complexes with long-lived charge-transfer excited states. No known iron complexes are considered12 photoluminescent at room temperature, and their rapid excited-state deactivation precludes their use as photosensitizers13,14,15. Here we present the iron complex [Fe(btz)3]3+ (where btz is 3,3′-dimethyl-1,1′-bis(p-tolyl)-4,4′-bis(1,2,3-triazol-5-ylidene)), and show that the superior σ-donor and π-acceptor electron properties of the ligand stabilize the excited state sufficiently to realize a long charge-transfer lifetime of 100 picoseconds (ps) and room-temperature photoluminescence. This species is a low-spin Fe(iii) d5 complex, and emission occurs from a long-lived doublet ligand-to-metal charge-transfer (2LMCT) state that is rarely seen for transition-metal complexes4,16,17. The absence of intersystem crossing, which often gives rise to large excited-state energy losses in transition-metal complexes, enables the observation of spin-allowed emission directly to the ground state and could be exploited as an increased driving force in photochemical reactions on surfaces. These findings suggest that appropriate design strategies can deliver new iron-based materials for use as light emitters and photosensitizers.
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| 3. |
- Chen, Junsheng, et al.
(författare)
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Excited-State Dynamics in a DNA-Stabilized Ag16 Cluster with Near-Infrared Emission
- 2023
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Ingår i: Journal of Physical Chemistry Letters. - 1948-7185. ; 14:17, s. 4078-4083
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Tidskriftsartikel (refereegranskat)abstract
- Due to desirable optical properties, such as efficient luminescence and large Stokes shift, DNA-templated silver nanoclusters (DNA-AgNCs) have received significant attention over the past decade. Nevertheless, the excited-state dynamics of these systems are poorly understood, as studies of the processes ultimately leading to a fluorescent state are scarce. Here we investigate the early time relaxation dynamics of a 16-atom silver cluster (DNA-Ag16NC) featuring NIR emission in combination with an unusually large Stokes shift of over 5000 cm-1. We follow the photoinduced dynamics of DNA-Ag16NC on time ranges from tens of femtoseconds to nanoseconds using a combination of ultrafast optical spectroscopies, and extract a kinetic model to clarify the physical picture of the photoinduced dynamics. We expect the obtained model to contribute to guiding research efforts toward elucidating the electronic structure and dynamics of these novel objects and their potential applications in fluorescence-based labeling, imaging, and sensing.
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| 4. |
- Nariyangadu, Sesha Bamini, et al.
(författare)
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New nonlinear optical crystal of rhodamine 590 acid phthalate
- 2020
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Ingår i: ACS Omega. - : American Chemical Society (ACS). - 2470-1343. ; 5:33, s. 20863-20873
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Tidskriftsartikel (refereegranskat)abstract
- The synthesis and crystal structure of rhodamine 590 acid phthalate (RhAP) have been reported. This novel solid-state rhodamine derivative not only has a longer fluorescence lifetime compared to rhodamine solid-state matrixes where emission is quenched but also possesses strong nonlinear optical characteristics. The static and dynamic first- and second-order hyperpolarizabilities were calculated using the time-dependent density functional theory at the B3LYP/6-31+G∗ level. The computed static values of β and γof RhAP by the X-ray diffraction (XRD) structure were 31.9 × 10-30 and 199.0 × 10-36 esu, respectively. These values were about 62 times larger than the corresponding values in urea, an already well-known nonlinear optical material. The second-order hyperpolarizability of the compound was determined experimentally by measuring the two-photon absorption cross section using intensity-modulated light fields. The reported compound, excitable at near-infrared, exhibited frequency upconversion with the two-photon absorption coefficient enhanced by two orders of magnitude compared to that of the dye solution. Hosting the dye in the solid, at high concentrations, exploits the nonlinearity of the dye itself as well as results in significant excitonic effects including formation of broad exciton band and superradiance.
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| 5. |
- Thyrhaug, Erling, et al.
(författare)
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Excited state kinetics of anthracene-bridge-aniline intramolecular exciplexes.
- 2014
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Ingår i: Photochemical and Photobiological Sciences. - : Springer Science and Business Media LLC. - 1474-9092 .- 1474-905X. ; 13:7, s. 1093-1105
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Tidskriftsartikel (refereegranskat)abstract
- We report on the synthesis and characterization of fluorescent halogen substituted anthracene-bridge-aniline (ABA) supermolecules that undergo structural reorganization on photoexcitation to form transient complexes. The syntheses were achieved in high yields on a large scale and the molecular structures were confirmed by single crystal X-ray diffraction. The photophysics of the ABA supermolecules were investigated using steady state and time resolved optical spectroscopy. Despite the presence of heavy atoms the series of ABA molecules have high quantum yields of fluorescence from both a locally excited anthracene state (LE) and an excited state complex (exciplex, EP) in non-polar solvents. The kinetics of the excited state processes were established in decalin from the time-resolved emission, and was shown to be strongly influenced by an electron-transfer state (ET). For quantitative studies of the excited state dynamics, the presence of this state required the development of a numerical three-excited-state kinetic model to replace the commonly used two-excited-state model. The experimental results shows that the reaction rates are strongly influenced both by substituents and solvent, illustrating the importance of including all relevant states in the kinetic modeling. Ultimately it is established that the excited state dynamics can conveniently be followed by optical methods, and the applicability of the system as a model system in time-resolved X-ray scattering experiments is discussed.
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| 6. |
- Thyrhaug, Erling, et al.
(författare)
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Exciton Structure and Energy Transfer in the Fenna-Matthews-Olson Complex
- 2016
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Ingår i: The Journal of Physical Chemistry Letters. - : American Chemical Society (ACS). - 1948-7185. ; 7:9, s. 1653-1660
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Tidskriftsartikel (refereegranskat)abstract
- The Fenna-Matthews-Olson (FMO) photosynthetic complex found in green sulfur bacteria has over the last decades been one of the favorite "model" systems for biological energy transfer. However, even after 40 years of studies, quantitative knowledge about its energy-transfer properties is limited. Here, two-dimensional electronic spectroscopy with full polarization control is used to provide an accurate description of the electronic structure and population dynamics in the complex. The sensitivity of the technique has further allowed us to spectroscopically identify the eighth bacterio-chlorophyll molecule recently discovered in the crystal structure. The time evolution of the spectral structure, covering time scales from tens of femtoseconds up to a nanosecond, reflects the energy flow in FMO and enables us to extract an unambiguous energy-transfer scheme.
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| 7. |
- Thyrhaug, Erling, et al.
(författare)
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Identification and characterization of diverse coherences in the Fenna–Matthews–Olson complex
- 2018
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Ingår i: Nature Chemistry. - : Springer Science and Business Media LLC. - 1755-4330 .- 1755-4349. ; 10:7, s. 780-786
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Tidskriftsartikel (refereegranskat)abstract
- The idea that excitonic (electronic) coherences are of fundamental importance to natural photosynthesis gained popularity when slowly dephasing quantum beats (QBs) were observed in the two-dimensional electronic spectra of the Fenna–Matthews–Olson (FMO) complex at 77 K. These were assigned to superpositions of excitonic states, a controversial interpretation, as the strong chromophore–environment interactions in the complex suggest fast dephasing. Although it has been pointed out that vibrational motion produces similar spectral signatures, a concrete assignment of these oscillatory signals to distinct physical processes is still lacking. Here we revisit the coherence dynamics of the FMO complex using polarization-controlled two-dimensional electronic spectroscopy, supported by theoretical modelling. We show that the long-lived QBs are exclusively vibrational in origin, whereas the dephasing of the electronic coherences is completed within 240 fs even at 77 K. We further find that specific vibrational coherences are produced via vibronically coupled excited states. The presence of such states suggests that vibronic coupling is relevant for photosynthetic energy transfer.
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| 8. |
- Thyrhaug, Erling, et al.
(författare)
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Intraband dynamics and exciton trapping in the LH2 complex of Rhodopseudomonas acidophila
- 2021
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Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 154:4
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Tidskriftsartikel (refereegranskat)abstract
- Over the last several decades, the light-harvesting protein complexes of purple bacteria have been among the most popular model systems for energy transport in excitonic systems in the weak and intermediate intermolecular coupling regime. Despite this extensive body of scientific work, significant questions regarding the excitonic states and the photo-induced dynamics remain. Here, we address the low-temperature electronic structure and excitation dynamics in the light-harvesting complex 2 of Rhodopseudomonas acidophila by two-dimensional electronic spectroscopy. We find that, although at cryogenic temperature energy relaxation is very rapid, exciton mobility is limited over a significant range of excitation energies. This points to the presence of a sub-200 fs, spatially local energy-relaxation mechanism and suggests that local trapping might contribute substantially more in cryogenic experiments than under physiological conditions where the thermal energy is comparable to or larger than the static disorder.
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| 9. |
- Thyrhaug, Erling, et al.
(författare)
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Ultrafast coherence transfer in DNA-templated silver nanoclusters
- 2017
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Ingår i: Nature Communications. - : Springer Science and Business Media LLC. - 2041-1723. ; 8
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Tidskriftsartikel (refereegranskat)abstract
- DNA-templated silver nanoclusters of a few tens of atoms or less have come into prominence over the last several years due to very strong absorption and efficient emission. Applications in microscopy and sensing have already been realized, however little is known about the excited-state structure and dynamics in these clusters. Here we report on a multidimensional spectroscopy investigation of the energy-level structure and the early-time relaxation cascade, which eventually results in the population of an emitting state. We find that the ultrafast intramolecular relaxation is strongly coupled to a specific vibrational mode, resulting in the concerted transfer of population and coherence between excited states on a sub-100 fs timescale.
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| 10. |
- Westerlund, Fredrik, 1978, et al.
(författare)
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Direct probing of ion pair formation using a symmetric triangulenium dye
- 2011
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Ingår i: Photochemical and Photobiological Sciences. - : Springer Science and Business Media LLC. - 1474-9092 .- 1474-905X. ; 10:12, s. 1963-1973
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Tidskriftsartikel (refereegranskat)abstract
- The 2,6,10-tris(dialkylamino)trioxatriangulenium dyes (ATOTA+) are highly stabilised cationic chromophores with D3h symmetry. The symmetry gives rise to a degeneracy of the main electronic transition. In low polarity solvents significant splitting of this degenerate transition is observed and assigned to ion pair formation. Ion pairing of the 2,6,10-tris(dioctylamino)trioxatriangulenium ionwith Cl-, BF4-, PF6- and TRISPHAT anions was studied using absorption spectroscopy. A clear correlation is found between the size of the anion and the splitting of the ATOTA+ transitions. In benzene the Cl- salt displays a splitting of 1955 cm-1, while the salt of the much larger TRISPHAT ionhas a splitting of 1543 cm-1. TD-DFT calculations confirm the splitting of the states and provide a detailed insight into the electronic structure of the ion pairs. The different degree of splitting in different ion pairs is found to correlate with the magnitude of the electric field generated in each ion pair, thus leading to the conclusion that the effect seen is an internal Stark effect. By insertion of an amphiphilic derivative of the ATOTA+ chromophore in an oriented lamellar liquid crystal, it was possible to resolve the two bands of the double peak spectrum and show their perpendicular orientation in the molecular framework, as predicted by the calculations.
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