| 1. |
- Abdellah, Mohamed, et al.
(författare)
-
Drastic difference between hole and electron injection through the gradient shell of CdxSeyZn1−xS1−y quantum dots
- 2017
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Ingår i: Nanoscale. - : Royal Society of Chemistry (RSC). - 2040-3364 .- 2040-3372. ; 9:34, s. 12503-12508
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Tidskriftsartikel (refereegranskat)abstract
- Ultrafast fluorescence spectroscopy was used to investigate the hole injection in CdxSeyZn1-xS1-y gradient core-shell quantum dot (CSQD) sensitized p-type NiO photocathodes. A series of CSQDs with a wide range of shell thicknesses was studied. Complementary photoelectrochemical cell measurements were carried out to confirm that the hole injection from the active core through the gradient shell to NiO takes place. The hole injection from the valence band of the QDs to NiO depends much less on the shell thickness when compared to the corresponding electron injection to n-type semiconductor (ZnO). We simulate the charge carrier tunneling through the potential barrier due to the gradient shell by numerically solving the Schrodinger equation. The details of the band alignment determining the potential barrier are obtained from X-ray spectroscopy measurements. The observed drastic differences between the hole and electron injection are consistent with a model where the hole effective mass decreases, while the gradient shell thickness increases.
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| 2. |
- Bamini, Sesha, et al.
(författare)
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Time-resolved terahertz spectroscopy reveals the influence of charged sensitizing quantum dots on the electron dynamics in ZnO
- 2017
-
Ingår i: Physical Chemistry Chemical Physics. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 19:8, s. 6006-6012
-
Tidskriftsartikel (refereegranskat)abstract
- Photoinitiated charge carrier dynamics in ZnO nanoparticles sensitized by CdSe quantum dots is studied using transient absorption spectroscopy and time-resolved terahertz spectroscopy. The evolution of the transient spectra shows that electron injection occurs in a two-step process, where the formation of a charge transfer state (occurring in several picoseconds) is followed by its dissociation within tens of picoseconds. The photoconductivity of electrons injected into the ZnO nanoparticles is lower than that of charges photogenerated directly in ZnO. We conclude that the motion of injected electrons in ZnO nanoparticles is strongly influenced by their interaction with positive charges left in the sensitizing quantum dots.
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| 3. |
- Becker, Christiane, et al.
(författare)
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Nanophotonic-Enhanced Two-Photon-Excited Photoluminescence of Perovskite Quantum Dots
- 2018
-
Ingår i: ACS Photonics. - : American Chemical Society (ACS). - 2330-4022. ; 5:11, s. 4668-4676
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Tidskriftsartikel (refereegranskat)abstract
- All-inorganic CsPbBr3 perovskite colloidal quantum dots have recently emerged as a promising material for a variety of optoelectronic applications, among others for multiphoton-pumped lasing. Nevertheless, high irradiance levels are generally required for such multiphoton processes. One strategy to enhance the multiphoton absorption is taking advantage of high local light intensities using photonic nanostructures. Here, we investigate two-photon-excited photoluminescence of CsPbBr3 perovskite quantum dots on a silicon photonic crystal slab. By systematic excitation of optical resonances using a pulsed near-infrared laser beam, we observe an enhancement of two-photon-pumped photoluminescence by more than 1 order of magnitude when comparing to using a bulk silicon film. Experimental and numerical analyses allow relating these findings to near-field enhancement effects on the nanostructured silicon surface. The results reveal a promising approach for significantly decreasing the required irradiance levels for multiphoton processes being of advantage in applications such as biomedical imaging, lighting, and solar energy.
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| 4. |
- Benazzi, Elisabetta, et al.
(författare)
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Acid-triggering of light-induced charge-separation in hybrid organic/inorganic molecular photoactive dyads for harnessing solar energy
- 2021
-
Ingår i: Inorganic Chemistry Frontiers. - : Royal Society of Chemistry (RSC). - 2052-1553. ; 8:6, s. 1610-1618
-
Tidskriftsartikel (refereegranskat)abstract
- H+ modulated charge-transfer in photoexcited covalent polyoxometalate-bodipy conjugates is described. The hybrid organic/inorganic molecular photoactive dyads are based on Keggin-type polyoxometalates (POMs, where KM = [PM11O39] and M = Mo or W) covalently grafted via an organotin linker to a bodipy (BOD) photosensitizer. The relative potentials of the photosensitizer and POM are aligned such that light-induced electron transfer from BOD to POM is permitted for the polyoxomolybdate KMoSn[BOD] but not effective for the polyoxotungstate analogue KWSn[BOD]. In both cases, the addition of acid shifts the redox potential of the POM only, to increase the driving force for electron transfer. This leads to charge-separation being switched on for KWSn[BOD] in the presence of acid. The addition of acid to KMoSn[BOD] accelerates charge-separation by an order of magnitude (from 2 ns to 200 ps) and is accompanied by a deceleration of charge recombination, leading to a charge-separated state lifetime of up to 1.3 μs. This behaviour is consistent with proton coupled electron transfer, which has previously been observed electrochemically for POMs, but this study shows, for the first time, the impact of protonation on photoinduced electron transfer. This journal is
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| 5. |
- Biasin, Elisa, et al.
(författare)
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Femtosecond X-Ray Scattering Study of Ultrafast Photoinduced Structural Dynamics in Solvated[Co(terpy)2]2$
- 2016
-
Ingår i: Physical Review Letters. - : American Physical Society (APS). - 1079-7114 .- 0031-9007. ; 117:1
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Tidskriftsartikel (refereegranskat)abstract
- We study the structural dynamics of photoexcited [Co(terpy)2]2+ in an aqueous solution with ultrafast x-ray diffuse scattering experiments conducted at the Linac Coherent Light Source. Through direct comparisons with density functional theory calculations, our analysis shows that the photoexcitation event leads to elongation of the Co-N bonds, followed by coherent Co-N bond length oscillations arising from the impulsive excitation of a vibrational mode dominated by the symmetrical stretch of all six Co-N bonds. This mode has a period of 0.33 ps and decays on a subpicosecond time scale. We find that the equilibrium bond-elongated structure of the high spin state is established on a single-picosecond time scale and that this state has a lifetime of ∼7 ps.
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| 6. |
- Canton, S. E., et al.
(författare)
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Watching the dynamics of electrons and atoms at work in solar energy conversion
- 2015
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Ingår i: Faraday discussions. - : Royal Society of Chemistry. - 1359-6640 .- 1364-5498. ; 185, s. 51-68
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Tidskriftsartikel (refereegranskat)abstract
- The photochemical reactions performed by transition metal complexes have been proposed as viable routes towards solar energy conversion and storage into other forms that can be conveniently used in our everyday applications. In order to develop efficient materials, it is necessary to identify, characterize and optimize the elementary steps of the entire process on the atomic scale. To this end, we have studied the photoinduced electronic and structural dynamics in two heterobimetallic ruthenium-cobalt dyads, which belong to the large family of donor-bridge-acceptor systems. Using a combination of ultrafast optical and X-ray absorption spectroscopies, we can clock the light-driven electron transfer processes with element and spin sensitivity. In addition, the changes in local structure around the two metal centers are monitored. These experiments show that the nature of the connecting bridge is decisive for controlling the forward and the backward electron transfer rates, a result supported by quantum chemistry calculations. More generally, this work illustrates how ultrafast optical and X-ray
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| 7. |
- Canton, Sophie, et al.
(författare)
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Toward Highlighting the Ultrafast Electron Transfer Dynamics at the Optically Dark Sites of Photocatalysts
- 2013
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Ingår i: The Journal of Physical Chemistry Letters. - : American Chemical Society (ACS). - 1948-7185. ; 4:11, s. 1972-1976
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Tidskriftsartikel (refereegranskat)abstract
- Building a detailed understanding of the structure function relationship is a crucial step in the optimization of molecular photocatalysts employed in water splitting schemes. The optically dark nature of their active sites usually prevents a complete mapping of the photoinduced dynamics. In this work, transient X-ray absorption spectroscopy highlights the electronic and geometric changes that affect such a center in a bimetallic model complex. Upon selective excitation of the ruthenium chromophore, the cobalt moiety is reduced through intramolecular electron transfer and undergoes a spin flip accompanied by an average bond elongation of 0.20 +/- 0.03 angstrom. The analysis is supported by simulations based on density functional theory structures (B3LYP*/TZVP) and FEFF 9.0 multiple scattering calculations. More generally, these results exemplify the large potential of the technique for tracking elusive intermediates that impart unique functionalities in photochemical devices.
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| 8. |
- Canton, Sophie, et al.
(författare)
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Visualizing the non-equilibrium dynamics of photoinduced intramolecular electron transfer with femtosecond X-ray pulses.
- 2015
-
Ingår i: Nature Communications. - : Springer Science and Business Media LLC. - 2041-1723. ; 6
-
Tidskriftsartikel (refereegranskat)abstract
- Ultrafast photoinduced electron transfer preceding energy equilibration still poses many experimental and conceptual challenges to the optimization of photoconversion since an atomic-scale description has so far been beyond reach. Here we combine femtosecond transient optical absorption spectroscopy with ultrafast X-ray emission spectroscopy and diffuse X-ray scattering at the SACLA facility to track the non-equilibrated electronic and structural dynamics within a bimetallic donor-acceptor complex that contains an optically dark centre. Exploiting the 100-fold increase in temporal resolution as compared with storage ring facilities, these measurements constitute the first X-ray-based visualization of a non-equilibrated intramolecular electron transfer process over large interatomic distances. Experimental and theoretical results establish that mediation through electronically excited molecular states is a key mechanistic feature. The present study demonstrates the extensive potential of femtosecond X-ray techniques as diagnostics of non-adiabatic electron transfer processes in synthetic and biological systems, and some directions for future studies, are outlined.
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| 9. |
- 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
-
Ingår i: Nature. - : Springer Science and Business Media LLC. - 0028-0836 .- 1476-4687. ; 543:7647, s. 695-699
-
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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| 10. |
- Chábera, Pavel, et al.
(författare)
-
Band-selective dynamics in charge-transfer excited iron carbene complexes
- 2019
-
Ingår i: Faraday Discussions. - : Royal Society of Chemistry (RSC). - 1359-6640 .- 1364-5498. ; 216:2019, s. 191-210
-
Tidskriftsartikel (refereegranskat)abstract
- Ultrafast dynamics of photoinduced charge transfer processes in light-harvesting systems based on Earth-abundant transition metal complexes are of current interest for the development of molecular devices for solar energy conversion applications. A combination of ultrafast spectroscopy and first principles quantum chemical calculations of a recently synthesized iron carbene complex is used to elucidate the ultrafast excited state evolution processes in these systems with particular emphasis on investigating the underlying reasons why these complexes show promise in terms of significantly extended lifetimes of charge transfer excited states. Together, our results challenge the traditional excited state landscape for iron-based light harvesting transition metal complexes through radically different ground and excited state properties in alternative oxidation states. This includes intriguing indications of rich band-selective excited state dynamics on ultrafast timescales that are interpreted in terms of excitation energy dependence for excitations into a manifold of charge-transfer states. Some implications of the observed excited state properties and photoinduced dynamics for the utilization of iron carbene complexes for solar energy conversion applications are finally discussed.
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| 11. |
- Chábera, Pavel, et al.
(författare)
-
FeII Hexa N-Heterocyclic Carbene Complex with a 528 ps Metal-To-Ligand Charge-Transfer Excited-State Lifetime
- 2018
-
Ingår i: Journal of Physical Chemistry Letters. - : American Chemical Society (ACS). - 1948-7185. ; 9:3, s. 459-463
-
Tidskriftsartikel (refereegranskat)abstract
- The iron carbene complex [FeII(btz)3](PF6)2 (where btz = 3,3′-dimethyl-1,1′-bis(p-Tolyl)-4,4′-bis(1,2,3-Triazol-5-ylidene)) has been synthesized, isolated, and characterized as a low-spin ferrous complex. It exhibits strong metal-To-ligand charge transfer (MLCT) absorption bands throughout the visible spectrum, and excitation of these bands gives rise to a 3MLCT state with a 528 ps excited-state lifetime in CH3CN solution that is more than one order of magnitude longer compared with the MLCT lifetime of any previously reported FeII complex. The low potential of the [Fe(btz)3]3+/[Fe(btz)3]2+ redox couple makes the 3MLCT state of [FeII(btz)3]2+ a potent photoreductant that can be generated by light absorption throughout the visible spectrum. Taken together with our recent results on the [FeIII(btz)3]3+ form of this complex, these results show that the FeII and FeIII oxidation states of the same Fe(btz)3 complex feature long-lived MLCT and LMCT states, respectively, demonstrating the versatility of iron N-heterocyclic carbene complexes as promising light-harvesters for a broad range of oxidizing and reducing conditions.
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| 12. |
- Chábera, Pavel, et al.
(författare)
-
Photofunctionality of iron(III) N-heterocyclic carbenes and related d5 transition metal complexes
- 2021
-
Ingår i: Coordination Chemistry Reviews. - : Elsevier BV. - 0010-8545. ; 426
-
Forskningsöversikt (refereegranskat)abstract
- Despite a few reports of photoluminescent and strongly photo-oxidizing transition metal complexes with a d5 electronic configuration, the photophysics and photochemistry of this class of transition metal complexes have largely remained unexplored. Recent investigations of earth-abundant iron(III) N-heterocyclic carbene (NHC) complexes have demonstrated promising photophysical and photochemical properties associated with low-spin (doublet) ligand-to-metal charge transfer (2LMCT) excitations, including nanosecond photoluminescence (PL) and capabilities to drive both photo-oxidation and photo-reduction reactions. These encouraging results are at first sight surprising in light of the general scarcity of known photofunctional complexes of any transition metal complexes with a d5 electronic configuration, including 1st, 2nd and 3rd row transition metal complexes of Mn(II), Tc(II), Re(II), Fe(III), Ru(III) and Os(III). Here, we review the photophysical and photochemical properties of the new Fe(III) NHC complexes together with related d5 transition metal complexes as a basis for a broader understanding of the unorthodox photophysical and photochemical properties associated with this open-shell electronic configuration. This includes considerations of the role of charge and spin effects on the ground state electronic structure, as well as discussions of charge transfer (CT) and metal centered (MC) excited state properties. The special properties of 2LMCT excited states are emphasized as a key feature to understand the photophysics of many photofunctional d5 transition metal complexes. Further aspects of excited state dynamics with d5 light-harvesting complexes, including both intra- and inter-molecular charge transfer processes, are also discussed. Finally, some fundamental challenges and emerging opportunities for further development of photofunctional Fe(III) NHC and related LMCT/d5 complexes for light-harvesting, light-emitting, and photo(electro)chemical applications are outlined. This includes some general considerations of how the specific photochemical properties of the LMCT/d5 complexes provides an exciting opportunity to develop a unique niche within the diversity of photofunctional molecular systems alongside other types of organic and inorganic chromophores commonly used in the field of molecular photochemistry.
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| 13. |
- Chen, Junsheng, et al.
(författare)
-
Enhanced Size Selection in Two-Photon Excitation for CsPbBr3 Perovskite Nanocrystals
- 2017
-
Ingår i: Journal of Physical Chemistry Letters. - : American Chemical Society (ACS). - 1948-7185. ; 8:20, s. 5119-5124
-
Tidskriftsartikel (refereegranskat)abstract
- Cesium lead bromide (CsPbBr3) perovskite nanocrystals (NCs), with large two-photon absorption (TPA) cross-section and bright photoluminescence (PL), have been demonstrated as stable two-photon-pumped lasing medium. With two-photon excitation, red-shifted PL spectrum and increased PL lifetime is observed compared with one-photon excitation. We have investigated the origin of such difference using time-resolved laser spectroscopies. We ascribe the difference to the enhanced size selection of NCs by two-photon excitation. Because of inherent nonlinearity, the size dependence of absorption cross-section under TPA is stronger. Consequently, larger size NCs are preferably excited, leading to longer excited-state lifetime and red-shifted PL emission. In a broad view, the enhanced size selection in two-photon excitation of CsPbBr3 NCs is likely a general feature of the perovskite NCs and can be tuned via NC size distribution to influence their performance within NC-based nonlinear optical materials and devices.
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| 14. |
- Chen, Junsheng, et al.
(författare)
-
Size-And Wavelength-Dependent Two-Photon Absorption Cross-Section of CsPbBr3 Perovskite Quantum Dots
- 2017
-
Ingår i: Journal of Physical Chemistry Letters. - : American Chemical Society (ACS). - 1948-7185. ; 8:10, s. 2316-2321
-
Tidskriftsartikel (refereegranskat)abstract
- All-inorganic colloidal perovskite quantum dots (QDs) based on cesium, lead, and halide have recently emerged as promising light emitting materials. CsPbBr3 QDs have also been demonstrated as stable two-photon-pumped lasing medium. However, the reported two photon absorption (TPA) cross sections for these QDs differ by an order of magnitude. Here we present an in-depth study of the TPA properties of CsPbBr3 QDs with mean size ranging from 4.6 to 11.4 nm. By using femtosecond transient absorption (TA) spectroscopy we found that TPA cross section is proportional to the linear one photon absorption. The TPA cross section follows a power law dependence on QDs size with exponent 3.3 ± 0.2. The empirically obtained power-law dependence suggests that the TPA process through a virtual state populates exciton band states. The revealed power-law dependence and the understanding of TPA process are important for developing high performance nonlinear optical devices based on CsPbBr3 nanocrystals.
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| 15. |
- Chen, Yani, et al.
(författare)
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Composition Engineering in Two-Dimensional Pb-Sn-Alloyed Perovskites for Efficient and Stable Solar Cells
- 2018
-
Ingår i: ACS Applied Materials and Interfaces. - : American Chemical Society (ACS). - 1944-8244 .- 1944-8252. ; 10:25, s. 21343-21348
-
Tidskriftsartikel (refereegranskat)abstract
- Environmentally friendly tin (Sn)-based metallic halide perovskites suffer from oxidation and morphological issues. Here, we demonstrate the composition engineering of Pb-Sn-alloyed two-dimensional (2D) Ruddlesden-Popper perovskites, (BA)2(MA)3Pb4-xSnxI13, for efficient and stable solar cell applications. Smooth thin films with high surface coverage are readily formed without using any additive owing to the self-assembly characteristic of 2D perovskites. It is found that Sn plays a significant role in improving the crystallization and crystal orientation while narrowing the bandgap of Pb-Sn 2D perovskites. Photophysical studies further reveal that the optimal Sn ratio (25 mol %) based sample exhibits both minimized trap density and weakened quantum confinement for efficient charge separation. Consequently, the optimized (BA)2(MA)3Pb3SnI13-based solar cells yield the best power conversion efficiency close to 6% with suppressed hysteresis.
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| 16. |
- Christensson, Niklas, et al.
(författare)
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Four-wave-mixing spectroscopy of peridinin in solution and in the peridinin-chlorophyll-a protein
- 2010
-
Ingår i: Chemical Physics. - : Elsevier BV. - 0301-0104. ; 373:1-2, s. 15-22
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Tidskriftsartikel (refereegranskat)abstract
- A model for the third order optical response of carotenoids is used to analyse transient grating and pump-probe data of peridinin in solution and bound in the peridinin-chlorophyll protein (PCP). For peridinin in solution, the transient grating signal detected at 505 nm exhibits a bi-exponential recovery whose fast phase is assigned to relaxation from the S-2 state that has a lifetime of 75 +/- 25 fs. The slower, solvent-dependent rise component is assigned to equilibration of the (S-1/ICT) state, taking place on a time scale of 0.6 and similar to 2.5 ps in acetontrile and benzene, respectively. These dynamics match those obtained from pump-probe measured in the spectral region of the ICT state, implying that the ICT state contributes to the signal at 505 nm. In PCP, the transient grating signal shows distinctly different kinetics, and the signal shows no recovery. This difference is explained by energy transfer from peridinin to chlorophyll-a. (C) 2009 Elsevier B. V. All rights reserved.
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| 17. |
- Dietzek, Benjamin, et al.
(författare)
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Optimal control of peridinin excited-state dynamics
- 2010
-
Ingår i: Chemical Physics. - : Elsevier BV. - 0301-0104. ; 373:1-2, s. 129-136
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Tidskriftsartikel (refereegranskat)abstract
- Optimal control is applied to study the excited-state relaxation of the carbonyl-carotenoid peridinin in solution. Phase-shaping of the excitation pulses is employed to influence the photoinduced reaction dynamics of peridinin. The outcome of various control experiments using different experimentally imposed fitness parameters is discussed. Furthermore, the effects of pump-wavelength and different solvents on the control efficiency are presented. The data show that excited-state population within either the S-1 or the ICT state can be reduced significantly by applying optimal control, while the efficiency of control decreases upon excitation into the low-energy side of the absorption band. However, we are unable to alter the ratio of S-1 and ICT population or increase the population of either state compared to excitation with a transform-limited pulse. We compare the results to various control mechanisms and argue that characteristic low-wavenumber modes are relevant for the photochemistry of peridinin. (C) 2010 Elsevier B. V. All rights reserved.
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| 18. |
- El Nahhas, Amal, et al.
(författare)
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Synthesis and Characterization of Cyclopentadithiophene Heterofulvenes : Design Tools for Light-Activated Processes
- 2017
-
Ingår i: Chemistry - A European Journal. - : Wiley. - 0947-6539 .- 1521-3765. ; 23:24, s. 5673-5677
-
Tidskriftsartikel (refereegranskat)abstract
- The development of new materials for solar-to-energy conversion should consider stability, ease of fabrication, and beneficial photophysical properties. In this context, a set of novel π-conjugated building blocks, with phospha- and arsaalkenes possessing a unique dithienyl annulated heterofulvenoid core, have been prepared as air- and moisture-stable sensitizers. These compounds unify electron-donor and -acceptor moieties, making them potential candidates for light-harvesting applications. Optical characterization of these systems was performed by steady-state and time-resolved absorption spectroscopy, supported by time-dependent DFT calculations. Tuning of the optical properties of these systems can be achieved by varying the pnictogen element at the bridgehead position, giving a bathochromic shift of ≈40 nm and coordinating the phosphaalkene towards gold AuI centers. The latter results in a ≈2000-fold extension of the ≈10 ps lifetime of uncoordinated systems well into the ns regime.
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| 19. |
- Ericson, Fredric, et al.
(författare)
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Electronic structure and excited state properties of iron carbene photosensitizers - A combined X-ray absorption and quantum chemical investigation
- 2017
-
Ingår i: Chemical Physics Letters. - : Elsevier BV. - 0009-2614. ; 683, s. 559-566
-
Tidskriftsartikel (refereegranskat)abstract
- The electronic structure and excited state properties of a series of iron carbene photosensitizers are elucidated through a combination of X-ray absorption measurements and density functional theory calculations. The X-ray absorption spectra are discussed with regard to the unusual bonding environment in these carbene complexes, highlighting the difference between ferrous and ferric carbene complexes. The valence electronic structure of the core excited FeIII-3d5 complex is predicted by calculating the properties of a CoIII-3d6 carbene complex using the Z+1 approximation. Insight is gained into the potential of sigma-donating ligands as strategy to tune properties for light harvesting applications.
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| 20. |
- Fredin, Lisa, et al.
(författare)
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Photochemistry of iron(III) carbenes
- 2017
-
Ingår i: Abstracts of Papers of the American Chemical Society. - : AMER CHEMICAL SOC. - 0065-7727. ; 254
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Tidskriftsartikel (övrigt vetenskapligt/konstnärligt)
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| 21. |
- Ghosh, Supriya, et al.
(författare)
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Slower Auger Recombination in 12-Faceted Dodecahedron CsPbBr3 Nanocrystals
- 2023
-
Ingår i: Journal of Physical Chemistry Letters. - : American Chemical Society (ACS). - 1948-7185. ; 14:4, s. 1066-1072
-
Tidskriftsartikel (refereegranskat)abstract
- Over the past two decades, intensive research efforts have been devoted to suppressions of Auger recombination in metal-chalcogenide and perovskite nanocrystals (PNCs) for the application of photovoltaics and light emitting devices (LEDs). Here, we have explored dodecahedron cesium lead bromide perovskite nanocrystals (DNCs), which show slower Auger recombination time compared to hexahedron nanocrystals (HNCs). We investigate many-body interactions that are manifested under high excitation flux density in both NCs using ultrafast spectroscopic pump-probe measurements. We demonstrate that the Auger recombination rate due to multiexciton recombinations are lower in DNCs than in HNCs. At low and intermediate excitation density, the majority of carriers recombine through biexcitonic recombination. However, at high excitation density (>1018 cm-3) a higher number of many-body Auger process dominates over biexcitonic recombination. Compared to HNCs, high PLQY and slower Auger recombinations in DNCs are likely to be significant for the fabrication of highly efficient perovskite-based photonics and LEDs.
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| 22. |
- Guo, Meiyuan, et al.
(författare)
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HERFD-XANES probes of electronic structures of ironII/IIIcarbene complexes
- 2020
-
Ingår i: Physical Chemistry Chemical Physics. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 22:16, s. 9067-9073
-
Tidskriftsartikel (refereegranskat)abstract
- Iron centeredN-heterocyclic carbene (Fe-NHC) complexes have shown long-lived excited states with charge transfer character useful for light harvesting applications. Understanding the nature of the metal-ligand bond is of fundamental importance to rationally tailor the properties of transition metal complexes. The high-energy-resolution fluorescence detected X-ray absorption near edge structure (HERFD-XANES) has been used to probe the valence orbitals of three carbene complexes, [FeII(bpy)(btz)2](PF6)2(bpy = 2,2′-bipyridine, btz = 3,3′-dimethyl-1,1′-bis(p-tolyl)-4,4′-bis(1,2,3-triazol-5-ylidene)), [FeIII(btz)3](PF6)3, and [FeIII(phtmeimb)2]PF6(phtmeimb = [phenyl(tris(3-methylimidazol-2-ylidene))borate]−). The multiconfigurational restrict active space (RAS) approach has been used to simulate the metal K pre-edge X-ray absorption spectroscopy of these carbene complexes, and have reproduced the metal K pre-edge spectral features in terms of relative intensity and peak positions. The evident intensity difference between the FeIIand the other two FeIIIcomplexes has been elucidated with different intensity mechanisms in the transition. The smaller splitting between the t2gand egcharacter peak for [FeIII(btz)3](PF6)3has been observed in the experimental measurements and been reproduced in the RAS calculations. The results show how the combination of experimental HERFD-XANES measurements andab initioRAS simulations can give quantitative evaluation of the orbital interactions between metal and ligands for such large and strongly interacting systems and thus allow to understand and predict properties of novel complexes.
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| 23. |
- Hammarström, Leif, et al.
(författare)
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Time-Resolved Laser Spectroscopy in Molecular Devices for Solar Energy Conversion
- 2017
-
Ingår i: Molecular Devices for Solar Energy Conversion and Storage. - Singapore : Springer Singapore. - 2196-6990 .- 2196-6982. - 9789811059230 - 9789811059247 ; , s. 385-432
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Bokkapitel (övrigt vetenskapligt/konstnärligt)abstract
- A complete characterization of solar energy conversion devices and the processes underlying their function is a challenge, and require a multitude of different experimental methods. This chapter discusses investigations of molecular solar cells and solar fuels devices by time-resolved laser spectroscopic methods. These methods have established important concepts we now use for understanding the function of devices for solar energy conversion into primary products. We give examples of scientific insight provided by ultrafast methods using detection in the regions from X-ray to THz radiation, and particularly highlight the case where the use of different methods has provided complementary information. Charge collection and solar fuel catalysis on the other hand occur on longer time scales, which opens for the use of time-resolved magnetic resonance and microwave conductivity methods. We also point out that, with suitable precautions, time-resolved laser spectroscopy is able to give information relevant for in operando device conditions
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| 24. |
- Hansen, Thorsten, et al.
(författare)
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Orbital Topology Controlling Charge Injection in Quantum-Dot-Sensitized Solar Cells
- 2014
-
Ingår i: The Journal of Physical Chemistry Letters. - : American Chemical Society (ACS). - 1948-7185. ; 5:7, s. 1157-1162
-
Tidskriftsartikel (refereegranskat)abstract
- Quantum-dot-sensitized solar cells are emerging as a promising development of dye-sensitized solar cells, where photostable semiconductor quantum dots replace molecular dyes. Upon photoexcitation of a quantum dot, an electron is transferred to a high-band-gap metal oxide. Swift electron transfer is crucial to ensure a high overall efficiency of the solar cell. Using femtosecond time-resolved spectroscopy, we find the rate of electron transfer to be surprisingly sensitive to the chemical structure of the linker molecules that attach the quantum dots to the metal oxide. A rectangular barrier model is unable to capture the observed variation. Applying bridge-mediated electron-transfer theory, we find that the electron-transfer rates depend on the topology of the frontier orbital of the molecular linker. This promises the capability of fine tuning the electron-transfer rates by rational design of the linker molecules.
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| 25. |
- Harlang, Tobias C. B., et al.
(författare)
-
Iron sensitizer converts light to electrons with 92% yield
- 2015
-
Ingår i: Nature Chemistry. - 1755-4330 .- 1755-4349. ; 7:11, s. 883-889
-
Tidskriftsartikel (refereegranskat)abstract
- Solar energy conversion in photovoltaics or photocatalysis involves light harvesting, or sensitization, of a semiconductor or catalyst as a first step. Rare elements are frequently used for this purpose, but they are obviously not ideal for large-scale implementation. Great efforts have been made to replace the widely used ruthenium with more abundant analogues like iron, but without much success due to the very short-lived excited states of the resulting iron complexes. Here, we describe the development of an iron-nitrogen-heterocyclic-carbene sensitizer with an excited-state lifetime that is nearly a thousand-fold longer than that of traditional iron polypyridyl complexes. By the use of electron paramagnetic resonance, transient absorption spectroscopy, transient terahertz spectroscopy and quantum chemical calculations, we show that the iron complex generates photoelectrons in the conduction band of titanium dioxide with a quantum yield of 92% from the 3MLCT (metal-to-ligand charge transfer) state. These results open up possibilities to develop solar energy-converting materials based on abundant elements.
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| 26. |
- Harlang, Tobias, et al.
(författare)
-
Iron sensitizer converts light to electrons with 92% yield.
- 2015
-
Ingår i: Nature Chemistry. - : Springer Science and Business Media LLC. - 1755-4330 .- 1755-4349. ; 7:11, s. 883-889
-
Tidskriftsartikel (refereegranskat)abstract
- Solar energy conversion in photovoltaics or photocatalysis involves light harvesting, or sensitization, of a semiconductor or catalyst as a first step. Rare elements are frequently used for this purpose, but they are obviously not ideal for large-scale implementation. Great efforts have been made to replace the widely used ruthenium with more abundant analogues like iron, but without much success due to the very short-lived excited states of the resulting iron complexes. Here, we describe the development of an iron-nitrogen-heterocyclic-carbene sensitizer with an excited-state lifetime that is nearly a thousand-fold longer than that of traditional iron polypyridyl complexes. By the use of electron paramagnetic resonance, transient absorption spectroscopy, transient terahertz spectroscopy and quantum chemical calculations, we show that the iron complex generates photoelectrons in the conduction band of titanium dioxide with a quantum yield of 92% from the (3)MLCT (metal-to-ligand charge transfer) state. These results open up possibilities to develop solar energy-converting materials based on abundant elements.
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| 27. |
- Hayashi, Hironobu, et al.
(författare)
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Effects of Immersion Solvent on Photovoltaic and Photophysical Properties of Porphyrin-Sensitized Solar Cells.
- 2015
-
Ingår i: ACS Applied Materials and Interfaces. - : American Chemical Society (ACS). - 1944-8244 .- 1944-8252. ; 7:33, s. 18689-18696
-
Tidskriftsartikel (refereegranskat)abstract
- Memory effects in self-assembled monolayers (SAMs) of zinc porphyrin carboxylic acid on TiO2 electrodes have been demonstrated for the first time by evaluating the photovoltaic and electron transfer properties of porphyrin-sensitized solar cells prepared by using different immersion solvents sequentially. The structure of the SAM of the porphyrin on the TiO2 was maintained even after treating the porphyrin monolayer with different neat immersion solvents (memory effect), whereas it was altered by treatment with solutions containing different porphyrins (inverse memory effect). Infrared spectroscopy shows that the porphyrins in the SAM on the TiO2 could be exchanged with the same or analogous porphyrin, leading to a change in the structure of the porphyrin SAM. The memory and inverse memory effects are well correlated with a change in porphyrin geometry, mainly the tilt angle of the porphyrin along the long molecular axis from the surface normal on the TiO2, as well as with kinetics of electron transfer between the porphyrin and TiO2. Such a new structure-function relationship for DSSCs will be very useful for the rational design and optimization of photoelectrochemical and photovoltaic properties of molecular assemblies on semiconductor surfaces.
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| 28. |
- He, Yanmei, et al.
(författare)
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Nature of Self-Trapped Exciton Emission in Zero-Dimensional Cs2ZrCl6 Perovskite Nanocrystals
- 2023
-
Ingår i: The Journal of Physical Chemistry Letters. - 1948-7185. ; 14:34, s. 7665-7671
-
Tidskriftsartikel (refereegranskat)abstract
- Low dimensional perovskite-inspired materials with self-tapped exciton (STE) emission have stimulated a surge of cutting-edge research in optoelectronics. Despite numerous efforts on developing versatile low-dimensional perovskite-inspired materials with efficient STE emissions, there is little emphasis on the intrinsic dynamics of STE-based broad emission in these materials. Here, we investigated the excited state dynamics in zero-dimensional (0D) Cs2ZrCl6 nanocrystals (NCs) with efficient blue STE emission. By using femtosecond transient absorption (fs-TA) spectroscopy, the ultrafast STE formation process within 400 fs is directly observed. Then, the formed STEs relax to an intermediate STE state with a lifetime of ∼180 ps before reaching the emissive STE state with a lifetime of ∼15 μs. Our work offers a comprehensive and precise dynamic picture of STE emission in low-dimensional metal halides and sheds light on extending their potential applications.
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| 29. |
- Honarfar, Alireza, et al.
(författare)
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Photoexcitation dynamics in electrochemically charged CdSe quantum dots : From hot carrier cooling to auger recombination of negative trions
- 2020
-
Ingår i: ACS Applied Energy Materials. - : American Chemical Society (ACS). - 2574-0962. ; 3:12, s. 12525-12531
-
Tidskriftsartikel (refereegranskat)abstract
- Fulfilling the potential of colloidal semiconductor quantum dots (QDs) in electrically driven applications remains a challenge largely since operation of such devices involves charged QDs with drastically different photophysical properties compared to their well-studied neutral counterparts. In this work, the full picture of excited state dynamics in charged CdSe QDs at various time scales has been revealed via transient absorption spectroscopy combined with electrochemistry as a direct manipulation tool to control the negative charging of CdSe QDs. In trions, excited states of single charged QDs, the additional electron in the conduction band speeds up the hot electron cooling by enhanced electron-electron scattering followed by charge redistribution and polaron formation in a picosecond time scale. The trions are finally decayed by the Auger process in a 500 ps time scale. Double charging in QDs, on the other hand, decelerates the polaron formation process while accelerates the following Auger decay. Our work demonstrates the potential of photoelectrochemistry as a platform for ultrafast spectroscopy of charged species and paves the way for further studies to develop comprehensive knowledge of the photophysical processes in charged QDs more than the well-known Auger decay, facilitating their use in future optoelectronic applications.
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| 30. |
- Honarfar, Alireza, et al.
(författare)
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Ultrafast dynamics in QD based photoelectrochemical cells
- 2019
-
Ingår i: Physical Chemistry of Semiconductor Materials and Interfaces XVIII. - : SPIE. - 9781510628618 ; 11084
-
Konferensbidrag (refereegranskat)abstract
- We have prepared electrodes for photo-electro-chemical cells which have enabled to pre-charge colloidal quantum dots in well-controlled fashion. Femtosecond transient absorption measurements were carried out revealing clear speed-up of the photo-induced charge carrier dynamics, particularly the recombination. Such studies allow to understand the behavior of light harvesting materials in operational conditions of optoelectronic devices giving new recipes for improvements.
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| 31. |
- Honarfar, Alireza, et al.
(författare)
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Ultrafast Spectroelectrochemistry Reveals Photoinduced Carrier Dynamics in Positively Charged CdSe Nanocrystals
- 2021
-
Ingår i: Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 125:26, s. 14332-14337
-
Tidskriftsartikel (refereegranskat)abstract
- Extra charges in semiconductor nanocrystals are of paramount importance for their electrically driven optoelectronic and photovoltaic applications. Optical excitations of such charged nanocrystals lead to rapid recombinationviaan Auger process, which can deteriorate the performance of the corresponding devices. While numerous articles report trion Auger processes in negatively charged nanocrystals, optical studies of well-controlled positive charging of nanocrystals and detailed studies of positive trions remain rare. In this work, we used electrochemistry to achieve positive charging of CdSe nanocrystals, so-called quantum dots (QDs), in a controlled way. Femtosecond transient absorption spectroscopy was applied forin situinvestigation of the charge carrier dynamics after optical excitation of the electrochemically charged QD assembly on TiO2. We observe that without bias (i.e., neutral QDs), sub-picosecond hot carrier cooling is followed by multiple phases of the dynamics corresponding to electron injection and transfer to the TiO2. Positive charging first leads to activation of the hole traps close to the valence band maximum, which opens a rapid recombination channel of the optical excitation. A further increase in the positive bias interrupts the electron injection to TiO2, and if nanocrystals are positively charged, it leads to Auger relaxation in a few hundred picosecond timescale. This study represents a step toward the understanding of the effect of positive charging on the performance of semiconductor nanocrystals under conditions which closely mimic their potential applications.
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| 32. |
- Huijser, Annemarie, et al.
(författare)
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Shedding Light on the Nature of Photoinduced States Formed in a Hydrogen-Generating Supramolecular RuPt Photocatalyst by Ultrafast Spectroscopy
- 2018
-
Ingår i: Journal of Physical Chemistry A. - : American Chemical Society (ACS). - 1089-5639 .- 1520-5215. ; 122:31, s. 6396-6406
-
Tidskriftsartikel (refereegranskat)abstract
- Photoinduced electronic and structural changes of a hydrogen-generating supramolecular RuPt photocatalyst are studied by a combination of time-resolved photoluminescence, optical transient absorption, and X-ray absorption spectroscopy. This work uses the element specificity of X-ray techniques to focus on the interplay between the photophysical and -chemical processes and the associated time scales at the catalytic Pt moiety. We observe very fast (<30 ps) photoreduction of the Pt catalytic site, followed by an ∼600 ps step into a strongly oxidized Pt center. The latter process is likely induced by oxidative addition of reactive iodine species. The oxidized Pt species is long-lived and fully recovers to the original ground state complex on a >10 μs time scale. However, the photosensitizing Ru moiety is fully restored on a much shorter ∼300 ns time scale. This reaction scheme implies that we may withdraw two electrons from a catalyst that is activated by a single photon.
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| 33. |
- Imahori, Hiroshi, et al.
(författare)
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Photoinduced Charge Carrier Dynamics of Zn-Porphyrin-TiO(2) Electrodes: The Key Role of Charge Recombination for Solar Cell Performance (†).
- 2011
-
Ingår i: Journal of physical chemistry. A. - : American Chemical Society (ACS). - 1520-5215 .- 1089-5639. ; 115:16, s. 3679-3690
-
Tidskriftsartikel (refereegranskat)abstract
- Time resolved absorption spectroscopy has been used to study photoinduced electron injection and charge recombination in Zn-porphyrin sensitized nanostructured TiO(2) electrodes. The electron transfer dynamics is correlated to the performance of dye sensitized solar cells based on the same electrodes. We find that the dye/semiconductor binding can be described with a heterogeneous geometry where the Zn-porphyrin molecules are attached to the TiO(2) surface with a distribution of tilt angles. The binding angle determines the porphyrin-semiconductor electron transfer distance and charge transfer occurs through space, rather than through the bridge connecting the porphyrin to the surface. For short sensitization times (1 h), there is a direct correlation between solar cell efficiency and amplitude of the kinetic component due to long-lived conduction band electrons, once variations in light harvesting (surface coverage) have been taken into account. Long sensitization time (12 h) results in decreased solar cell efficiency because of decreased efficiency of electron injection.
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| 34. |
- Kaufhold, Simon, et al.
(författare)
-
Microsecond Photoluminescence and Photoreactivity of a Metal-Centered Excited State in a Hexacarbene-Co(III) Complex
- 2021
-
Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; , s. 1307-1312
-
Tidskriftsartikel (refereegranskat)abstract
- The photofunctionality of the cobalt-hexacarbene complex [Co(III)(PhB(MeIm)3)2]+ (PhB(MeIm)3 = tris(3-methylimidazolin-2-ylidene)(phenyl)borate) has been investigated by time-resolved optical spectroscopy. The complex displays a weak (φ ∼10-4) but remarkably long-lived (τ ∼1 μs) orange photoluminescence at 690 nm in solution at room temperature following excitation with wavelengths shorter than 350 nm. The strongly red-shifted emission is assigned from the spectroscopic evidence and quantum chemical calculations as a rare case of luminescence from a metal-centered state in a 3d6 complex. Singlet oxygen quenching supports the assignment of the emitting state as a triplet metal-centered state and underlines its capability of driving excitation energy transfer processes.
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| 35. |
- Keşan, Gürkan, et al.
(författare)
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Time-Resolved Spectroelectrochemical Dynamics of Carotenoid 8’-apo-β-Carotenal
- 2023
-
Ingår i: ChemPlusChem. - 2192-6506. ; 88:11
-
Tidskriftsartikel (refereegranskat)abstract
- This work examines the influence of applied external voltage in bulk electrolysis on the excited-state properties of 8′-apo-β-carotenal in acetonitrile by steady-state and ultrafast time-resolved absorption spectroscopy. The data collected under bulk electrolysis were compared with those taken without applied voltage. The steady-state measurements showed that although intensity of the S0-S2 absorption band varies with the applied voltage, the spectral position remain nearly constant. Comparison of transient absorption spectra shows that the magnitude of the ICT-like band decreases during the experiment under applied voltage condition, and is associated with a prolongation of the S1/ICT-like lifetime from 8 ps to 13 ps. Furthermore, switching off the applied voltage resulted in returning to no-voltage data within about 30 min. Our results show that the amplitude of the signal associated with the ICT state can be tuned by applying an external voltage.
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| 36. |
- Kjær, Kasper S., et al.
(författare)
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Finding intersections between electronic excited state potential energy surfaces with simultaneous ultrafast X-ray scattering and spectroscopy
- 2019
-
Ingår i: Chemical Science. - : Royal Society of Chemistry (RSC). - 2041-6520 .- 2041-6539. ; 10:22, s. 5749-5760
-
Tidskriftsartikel (refereegranskat)abstract
- Light-driven molecular reactions are dictated by the excited state potential energy landscape, depending critically on the location of conical intersections and intersystem crossing points between potential surfaces where non-adiabatic effects govern transition probabilities between distinct electronic states. While ultrafast studies have provided significant insight into electronic excited state reaction dynamics, experimental approaches for identifying and characterizing intersections and seams between electronic states remain highly system dependent. Here we show that for 3d transition metal systems simultaneously recorded X-ray diffuse scattering and X-ray emission spectroscopy at sub-70 femtosecond time-resolution provide a solid experimental foundation for determining the mechanistic details of excited state reactions. In modeling the mechanistic information retrieved from such experiments, it becomes possible to identify the dominant trajectory followed during the excited state cascade and to determine the relevant loci of intersections between states. We illustrate our approach by explicitly mapping parts of the potential energy landscape dictating the light driven low-to-high spin-state transition (spin crossover) of [Fe(2,2′-bipyridine)3]2+, where the strongly coupled nuclear and electronic dynamics have been a source of interest and controversy. We anticipate that simultaneous X-ray diffuse scattering and X-ray emission spectroscopy will provide a valuable approach for mapping the reactive trajectories of light-triggered molecular systems involving 3d transition metals.
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| 37. |
- Kjær, Kasper Skov, et al.
(författare)
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Luminescence and reactivity of a charge-transfer excited iron complex with nanosecond lifetime
- 2019
-
Ingår i: Science. - : American Association for the Advancement of Science (AAAS). - 0036-8075 .- 1095-9203. ; 363:6424, s. 249-253
-
Tidskriftsartikel (refereegranskat)abstract
- Iron’s abundance and rich coordination chemistry are potentially appealing features for photochemical applications. However, the photoexcitable charge-transfer (CT) states of most Fe complexes are limited by picosecond or sub-picosecond deactivation through low-lying metal centered (MC) states, resulting in inefficient electron transfer reactivity and complete lack of photoluminescence. Here we show that octahedral coordination of Fe(III) by two mono-anionic facial tris-carbene ligands can suppress such deactivation dramatically. The resulting complex [Fe(phtmeimb)2]+, where phtmeimb is [phenyl(tris(3-methylimidazol-1-ylidene))borate]-, exhibits strong, visible, room temperature photoluminescence with a 2.0 ns lifetime and 2% quantum yield via spin-allowed transition from a ligand-to-metal charge-transfer (2 LMCT) state to the ground state (2 GS). Reductive and oxidative electron transfer reactions were observed for the2 LMCT state of [Fe(phtmeimb)2]+ in bimolecular quenching studies with methylviologen and diphenylamine.
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| 38. |
- Kjær, Kasper S., et al.
(författare)
-
Solvent control of charge transfer excited state relaxation pathways in [Fe(2,2′-bipyridine)(CN)4]2-
- 2018
-
Ingår i: Physical Chemistry Chemical Physics. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 20:6, s. 4238-4249
-
Tidskriftsartikel (refereegranskat)abstract
- The excited state dynamics of solvated [Fe(bpy)(CN)4]2-, where bpy = 2,2′-bipyridine, show significant sensitivity to the solvent Lewis acidity. Using a combination of optical absorption and X-ray emission transient spectroscopies, we have previously shown that the metal to ligand charge transfer (MLCT) excited state of [Fe(bpy)(CN)4]2- has a 19 picosecond lifetime and no discernable contribution from metal centered (MC) states in weak Lewis acid solvents, such as dimethyl sulfoxide and acetonitrile.1,2 In the present work, we use the same combination of spectroscopic techniques to measure the MLCT excited state relaxation dynamics of [Fe(bpy)(CN)4]2- in water, a strong Lewis acid solvent. The charge-transfer excited state is now found to decay in less than 100 femtoseconds, forming a quasi-stable metal centered excited state with a 13 picosecond lifetime. We find that this MC excited state has triplet (3MC) character, unlike other reported six-coordinate Fe(ii)-centered coordination compounds, which form MC quintet (5MC) states. The solvent dependent changes in excited state non-radiative relaxation for [Fe(bpy)(CN)4]2- allows us to infer the influence of the solvent on the electronic structure of the complex. Furthermore, the robust characterization of the dynamics and optical spectral signatures of the isolated 3MC intermediate provides a strong foundation for identifying 3MC intermediates in the electronic excited state relaxation mechanisms of similar Fe-centered systems being developed for solar applications.
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| 39. |
- Kunnus, Kristjan, et al.
(författare)
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Vibrational wavepacket dynamics in Fe carbene photosensitizer determined with femtosecond X-ray emission and scattering
- 2020
-
Ingår i: Nature Communications. - : Springer Nature. - 2041-1723. ; 11:1
-
Tidskriftsartikel (refereegranskat)abstract
- The non-equilibrium dynamics of electrons and nuclei govern the function of photoactive materials. Disentangling these dynamics remains a critical goal for understanding photoactive materials. Here we investigate the photoinduced dynamics of the [Fe(bmip)2]2+ photosensitizer, where bmip = 2,6-bis(3-methyl-imidazole-1-ylidine)-pyridine, with simultaneous femtosecond-resolution Fe Kα and Kβ X-ray emission spectroscopy (XES) and X-ray solution scattering (XSS). This measurement shows temporal oscillations in the XES and XSS difference signals with the same 278 fs period oscillation. These oscillations originate from an Fe-ligand stretching vibrational wavepacket on a triplet metal-centered (3MC) excited state surface. This 3MC state is populated with a 110 fs time constant by 40% of the excited molecules while the rest relax to a 3MLCT excited state. The sensitivity of the Kα XES to molecular structure results from a 0.7% average Fe-ligand bond length shift between the 1 s and 2p core-ionized states surfaces.
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| 40. |
- Kurotobi, Kei, et al.
(författare)
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Highly Asymmetrical Porphyrins with Enhanced Push-Pull Character for Dye-Sensitized Solar Cells
- 2013
-
Ingår i: Chemistry: A European Journal. - : Wiley. - 1521-3765 .- 0947-6539. ; 19:50, s. 17075-17081
-
Tidskriftsartikel (refereegranskat)abstract
- A porphyrin -system has been modulated by enhancing the push-pull character with highly asymmetrical substitution for dye-sensitized solar cells for the first time. Namely, both two diarylamino moieties as a strong electron-donating group and one carboxyphenylethynyl moiety as a strong electron-withdrawing, anchoring group were introduced into the meso-positions of the porphyrin core in a lower symmetrical manner. As a result of the improved light-harvesting property as well as high electron distribution in the anchoring group of LUMO, a push-pull-enhanced, porphyrin-sensitized solar cell exhibited more than 10% power conversion efficiency, which exceeded that of a representative highly efficient porphyrin (i.e., YD2)-sensitized solar cell under optimized conditions. The rational molecular design concept based on highly asymmetric, push-pull substitution will open the possibilities of further improving cell performance in organic solar cells.
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| 41. |
- Kuznetsova, Valentyna, et al.
(författare)
-
Effect of Isomerization on Excited-State Dynamics of Carotenoid Fucoxanthin
- 2017
-
Ingår i: Journal of Physical Chemistry B. - : American Chemical Society (ACS). - 1520-6106 .- 1520-5207. ; 121:17, s. 4438-4447
-
Tidskriftsartikel (refereegranskat)abstract
- Ultrafast transient absorption spectroscopy and single-wavelength anisotropy measurements were used to study the effect of isomerization on the excited-state properties of fucoxanthin in polar and nonpolar solvents. The excitation wavelengths were 477 nm for all-trans-fucoxanthin, and 333 and 477 nm for cis-fucoxanthin. All transient absorption spectra of the fucoxanthin isomers in polar solvents show intramolecular charge transfer (ICT) state features, typical for carbonyl carotenoids. Global analysis of the data requires an additional fitting component, originated from the presence of blue and red forms of fucoxanthin in a polar protic solvent. Here we demonstrate that the ICT state decays faster than the S1 state, due to the significant contribution of the red form to the ICT state dynamics. The isomerization does not affect the S1 lifetime, but induces a larger difference between the S1- and ICT-state lifetimes in cis-fucoxanthin, which is likely caused by alterations of ICT coupling to either the S1 or S0 states; the S∗-state signal is more pronounced for cis-isomers in a nonpolar solvent.
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| 42. |
- Lindh, Linnea, et al.
(författare)
-
Dye-sensitized solar cells based on Fe N-heterocyclic carbene photosensitizers with improved rod-like push-pull functionality
- 2021
-
Ingår i: Chemical Science. - : Royal Society of Chemistry (RSC). - 2041-6520 .- 2041-6539. ; 12:48, s. 16035-16053
-
Tidskriftsartikel (refereegranskat)abstract
- A new generation of octahedral iron(ii)-N-heterocyclic carbene (NHC) complexes, employing different tridentate C^N^C ligands, has been designed and synthesized as earth-abundant photosensitizers for dye sensitized solar cells (DSSCs) and related solar energy conversion applications. This work introduces a linearly aligned push-pull design principle that reaches from the ligand having nitrogen-based electron donors, over the Fe(ii) centre, to the ligand having an electron withdrawing carboxylic acid anchor group. A combination of spectroscopy, electrochemistry, and quantum chemical calculations demonstrate the improved molecular excited state properties in terms of a broader absorption spectrum compared to the reference complex, as well as directional charge-transfer displacement of the lowest excited state towards the semiconductor substrate in accordance with the push-pull design. Prototype DSSCs based on one of the new Fe NHC photosensitizers demonstrate a power conversion efficiency exceeding 1% already for a basic DSSC set-up using only the I−/I3−redox mediator and standard operating conditions, outcompeting the corresponding DSSC based on the homoleptic reference complex. Transient photovoltage measurements confirmed that adding the co-sensitizer chenodeoxycholic acid helped in improving the efficiency by increasing the electron lifetime in TiO2. Time-resolved spectroscopy revealed spectral signatures for successful ultrafast (<100 fs) interfacial electron injection from the heteroleptic dyes to TiO2. However, an ultrafast recombination process results in undesirable fast charge recombination from TiO2back to the oxidized dye, leaving only 5-10% of the initially excited dyes available to contribute to a current in the DSSC. On slower timescales, time-resolved spectroscopy also found that the recombination dynamics (longer than 40 μs) were significantly slower than the regeneration of the oxidized dye by the redox mediator (6-8 μs). Therefore it is the ultrafast recombination down to fs-timescales, between the oxidized dye and the injected electron, that remains as one of the main bottlenecks to be targeted for achieving further improved solar energy conversion efficiencies in future work.
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| 43. |
- Lindh, Linnea, et al.
(författare)
-
Multifaceted Deactivation Dynamics of Fe(II) N-Heterocyclic Carbene Photosensitizers
- 2023
-
Ingår i: Journal of Physical Chemistry A. - 1089-5639. ; 127:48, s. 10210-10222
-
Tidskriftsartikel (refereegranskat)abstract
- Excited state dynamics of three iron(II) carbene complexes that serve as prototype Earth-abundant photosensitizers were investigated by ultrafast optical spectroscopy. Significant differences in the dynamics between the investigated complexes down to femtosecond time scales are used to characterize fundamental differences in the depopulation of triplet metal-to-ligand charge-transfer (3MLCT) excited states in the presence of energetically accessible triplet metal-centered (3MC) states. Novel insights into the full deactivation cascades of the investigated complexes include evidence of the need to revise the deactivation model for a prominent iron carbene prototype complex, a refined understanding of complex 3MC dynamics, and a quantitative discrimination between activated and barrierless deactivation steps along the 3MLCT → 3MC → 1GS path. Overall, the study provides an improved understanding of photophysical limitations and opportunities for the use of iron(II)-based photosensitizers in photochemical applications.
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| 44. |
- Lindh, Linnea, et al.
(författare)
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Photophysics and photochemistry of iron carbene complexes for solar energy conversion and photocatalysis
- 2020
-
Ingår i: Catalysts. - : MDPI AG. - 2073-4344. ; 10:3
-
Forskningsöversikt (refereegranskat)abstract
- Earth-abundant first row transition metal complexes are important for the development of large-scale photocatalytic and solar energy conversion applications. Coordination compounds based on iron are especially interesting, as iron is the most common transition metal element in the Earth’s crust. Unfortunately, iron-polypyridyl and related traditional iron-based complexes generally suffer from poor excited state properties, including short excited-state lifetimes, that make them unsuitable for most light-driven applications. Iron carbene complexes have emerged in the last decade as a new class of coordination compounds with significantly improved photophysical and photochemical properties, that make them attractive candidates for a range of light-driven applications. Specific aspects of the photophysics and photochemistry of these iron carbenes discussed here include long-lived excited state lifetimes of charge transfer excited states, capabilities to act as photosensitizers in solar energy conversion applications like dye-sensitized solar cells, as well as recent demonstrations of promising progress towards driving photoredox and photocatalytic processes. Complementary advances towards photofunctional systems with both Fe(II) complexes featuring metal-to-ligand charge transfer excited states, and Fe(III) complexes displaying ligand-to-metal charge transfer excited states are discussed. Finally, we outline emerging opportunities to utilize the improved photochemical properties of iron carbenes and related complexes for photovoltaic, photoelectrochemical and photocatalytic applications.
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| 45. |
- Lindh, Linnea, et al.
(författare)
-
Side-group switching between metal-to-ligand charge-transfer and metal-centered excited state properties in iron(II) N-heterocyclic carbene complexes
- 2024
-
Ingår i: Coordination Chemistry Reviews. - 0010-8545. ; 506
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Forskningsöversikt (refereegranskat)abstract
- Fe(II) N-heterocyclic carbene (NHC) complexes have emerged over the last decade as a promising class of light-harvesting complexes for a variety of photochemical applications relying on the presence of high-energy excited states of mainly charge-transfer character with excited state lifetimes of tens of picoseconds or longer. Recent spectroscopic investigations have significantly refined the understanding of some of the key prototype complexes of this kind and highlighted the subtle balance between population of triplet metal-to-ligand charge-transfer (3MLCT) and triplet metal-centered (3MC) states as a key issue to better understand and ultimately control the excited state dynamics in these complexes. To present a broader perspective on this issue, we here re-examine and discuss the excited state properties of a series of complexes with different side-groups on a common Fe NHC scaffold. Both the steady-state absorption spectrum and excited state dynamics are influenced by the side-group substitution, and the changes are rationalized based on shifting of the lowest metal-to-ligand charge-transfer (MLCT) state in energy based on the electron-withdrawing or electron-donating properties of the side-groups. Only electron-withdrawing substituents such as carboxylic acid groups ensured that the majority excited population stays in the 3MLCT state for ∼20 ps rather than rapidly converting into metal-centered (MC) states. In other complexes, the 3MLCT state survived <300 fs after which the 3MC state was populated for ∼10 ps. The transient absorption results also show that the dynamics can be switched in a simple manner by deprotonating the carboxylic acid group, which renders some of the complexes pH-sensitive. For the here discussed complexes, the results from transient absorption measurements indicate that the 3MLCT and 3MC states were close enough in energy to enable the side-group to determine the photophysics. The emerging understanding of the 3MLCT-3MC balance, as well as the nature and properties of the 3MC state in these complexes with intermediate ligand field strength is used to provide a broader fundamental perspective required to improve the ligand-design of Fe carbene complexes for issues such as to ensure a long-lived 3MLCT state.
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| 48. |
- Lunden, Hampus, et al.
(författare)
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An optical power limiting and ultrafast photophysics investigation of a series of multi-branched heavy atom substituted fluorene molecules
- 2019
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Ingår i: Inorganics. - : MDPI AG. - 2304-6740. ; 7:10
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Tidskriftsartikel (refereegranskat)abstract
- A common molecular design paradigm for optical power limiting (OPL) applications is to introduce heavy atoms that promote intersystem crossing and triplet excited states. In order to investigate this effect, three multi-branched fluorene molecules were prepared where the central moiety was either an organic benzene unit, para-dibromobenzene, or a platinum(II)-alkynyl unit. All three molecules showed good nanosecond OPL performance in solution. However, only the dibromobenzene and Pt-alkynyl compounds showed strong microsecond triplet excited state absorption (ESA). To investigate the photophysical cause of the OPL, especially for the fully organic molecule, photokinetic measurements including ultrafast pump-probe spectroscopy were performed. At nanosecond timescales, the ESA of the organic molecule was larger than the two with intersystem crossing (ISC) promoters, explaining its good OPL performance. This points to a design strategy where the singlet-state ESA is balanced with the ISC rate to increase OPL performance at the beginning of a nanosecond pulse.
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| 49. |
- Müller, Carolin, et al.
(författare)
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KiMoPack : A python Package for Kinetic Modeling of the Chemical Mechanism
- 2022
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Ingår i: Journal of Physical Chemistry A. - : American Chemical Society (ACS). - 1089-5639 .- 1520-5215. ; 126:25, s. 4087-4099
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Tidskriftsartikel (refereegranskat)abstract
- Herein, we present KiMoPack, an analysis tool for the kinetic modeling of transient spectroscopic data. KiMoPack enables a state-of-the-art analysis routine including data preprocessing and standard fitting (global analysis), as well as fitting of complex (target) kinetic models, interactive viewing of (fit) results, and multiexperiment analysis via user accessible functions and a graphical user interface (GUI) enhanced interface. To facilitate its use, this paper guides the user through typical operations covering a wide range of analysis tasks, establishes a typical workflow and is bridging the gap between ease of use for less experienced users and introducing the advanced interfaces for experienced users. KiMoPack is open source and provides a comprehensive front-end for preprocessing, fitting and plotting of 2-dimensional data that simplifies the access to a powerful python-based data-processing system and forms the foundation for a well documented, reliable, and reproducible data analysis.
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| 50. |
- Polivka, Tomas, et al.
(författare)
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Carotenoid-protein interaction alters the S-1 energy of hydroxyechinenone in the Orange Carotenoid Protein
- 2013
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Ingår i: Biochimica et Biophysica Acta - Bioenergetics. - : Elsevier BV. - 0005-2728. ; 1827:3, s. 248-254
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Tidskriftsartikel (refereegranskat)abstract
- The Orange Carotenoid Protein (OCP) is a photoactive water soluble protein that is crucial for photoprotection in cyanobacteria. When activated by blue-green light, it triggers quenching of phycobilisome fluorescence and regulates energy flow from the phycobilisome to the reaction center. The OCP contains a single pigment, the carotenoid 3'-hydroxyechinenone (hECN). Binding to the OCP causes a conformational change in hECN leading to an extension of its effective conjugation length. We have determined the S-1 energy of hECN in organic solvent and compared it with the S-1 energy of hECN bound to the OCP. In methanol and n-hexane, hECN has an S-1 energy of 14,300 cm(-1), slightly higher than carotenoids with shorter conjugation lengths such as zeaxanthin or beta-carotene; this is consistent with the proposal that the presence of the conjugated carbonyl group in hECN increases its Si energy. The S-1 energy of hECN in organic solvent is independent of solvent polarity. Upon binding to the OCP, the S-1 energy of hECN is further increased to 14,700 cm(-1), underscoring the importance of protein binding which twists the conjugated carbonyl group into s-trans conformation and enhances the effect of the carbonyl group. Activated OCP, however, has an S-1 energy of 14,000 cm(-1), indicating that significant changes in the vicinity of the conjugated carbonyl group occur upon activation. (C) 2012 Elsevier B.V. All rights reserved.
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