1. |
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2. |
- Aarnio, Harri, et al.
(author)
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Recombination studies in a polyfluorene copolymer for photovoltaic applications
- 2005
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In: Synthetic Metals. - : Elsevier BV. - 0379-6779. ; 155:2, s. 299-302
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Journal article (peer-reviewed)abstract
- We present detailed continuous wave (cw) and transient photoinduced absorption (PA) measurements in thin films of a novel alternating polyfluorene copolymer, poly[2,7-(9,9-dioctyl-fluorene)-alt-5,5-(4',7'-di-2-thienyl-2',1',3-benzo-thiadiazole)] (DiO-PFDTBT), and its blends with the sol. fullerene deriv. [6,6]-phenyl-C61-butyric acid Me ester (PCBM) in wt. ratios of 1:0, 4:1 and 1:4. We measure the frequency, intensity and temp. dependence of the PA signal in the frequency domain, and compare with the results obtained from the transient PA decay measurements in the time domain. In all blends, the PA spectrum shows a broad high energy PA band ranging from .apprx.1 eV to 2 eV as well as a low energy band peaking at .apprx.0.35 eV. We attribute the low energy band to the P1 transition of polarons and part of the high energy band to the correlated P2 transition of polarons. Both frequency and time domain measurements show that the high energy band has two decay components, a faster component in the microsecond time regime and a slower component in the millisecond time regime. The slow component is strongly dispersive, whereas the fast component is practically non-dispersive. [on SciFinder (R)]
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3. |
- Andersson, Johan, et al.
(author)
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New paradigm of transition metal polypyridine complex photochemistry
- 2004
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In: Faraday Discussions. - : Royal Society of Chemistry (RSC). - 1364-5498. ; 127, s. 295-305
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Journal article (peer-reviewed)abstract
- Using polarization sensitive ultrafast transient absorption spectroscopy we have studied energy transfer and excited state relaxation pathways in a tetranuclear transition metal [( osmium)( ruthenium)(3)] polypyridine complex. Contrary to the generally accepted picture of transition metal complex photochemistry we find that ultrafast energy transfer ( less than or equal to 60 fs) occurs from the excited singlet MLCT state of the peripheral Ru-chromophores to the central Os-core, in efficient competition with intersystem crossing. Energy transfer between relaxed triplet MLCT states is more than an order of magnitude slower ( 600 fs).
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4. |
- Andersson, Johan, et al.
(author)
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Ultrafast singlet energy transfer competes with intersystem crossing in a multi-center transition metal polypyridine complex
- 2004
-
In: Chemical Physics Letters. - : Elsevier BV. - 0009-2614. ; 386:4-6, s. 336-341
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Journal article (peer-reviewed)abstract
- Transition metal polypyridine complexes are finding widespread applications within many areas of chemistry. For their light-induced processes, the generally accepted picture is that all function emanates from triplet states because the singlet states initially prepared by light absorption are depopulated via intersystem crossing on the 100-fs time scale, before they are significantly involved in chemical reactions. Here we show that this is not always true. With ultrafast spectroscopy applied to a (ruthenium)(3)-osmium complex we show that transition metal polypyridine complexes can be designed where energy transfer between excited singlet states located on different metal centers efficiently competes with intersystem crossing, thus decreasing population of the lower-lying triplet states and concomitant energy loss. (C) 2004 Elsevier B.V. All rights reserved.
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5. |
- Billsten, Helena, et al.
(author)
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Excited-state processes in the carotenoid zeaxanthin after excess energy excitation
- 2005
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In: The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory. - : American Chemical Society (ACS). - 1520-5215. ; 109:31, s. 6852-6859
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Journal article (peer-reviewed)abstract
- Aiming for better understanding of the large complexity of excited-state processes in carotenoids, we have studied the excitation wavelength dependence of the relaxation dynamics in the carotenoid zeaxanthin. Excitation into the lowest vibrational band of the S-2 state at 485 nm, into the 0-3 vibrational band of the S2 state at 400 nm, and into the B-2(u)+ state at 266 nm resulted in different relaxation patterns. While excitation at 485 nm produces the known four-state scheme (S-2 -> hot S-1 -> S-1 -> S-0), excess energy excitation led to additional dynamics occurring with a time constant of 2.8 ps (400 nm excitation) and 4.9 ps (266 nm excitation), respectively. This process is ascribed to a conformational relaxation of conformers generated by the excess energy excitation. The zeaxanthin S* state was observed regardless of the excitation wavelength, but its population increased after 400 and 266 nm excitation, suggesting that conformers generated by the excess energy excitation are important for directing the population toward the S* state. The S-2-S-1 internal conversion time was shortened from 135 to 70 fs when going from 485 to 400 nm excitation, as a result of competition between the S-2-S-1 internal conversion from the vibrationally hot S2 state and S2 vibrational relaxation. The S, lifetime of zeaxanthin was within experimental error the same for all excitation wavelengths, yielding similar to 9 ps. No long-lived species have been observed after excitation by femtosecond pulses regardless of the excitation wavelength, but excitation by nanosecond pulses at 266 nm generated both zeaxanthin triplet state and cation radical.
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6. |
- Brüggemann, Ben, et al.
(author)
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Control of electron transfer pathways in a dye-sensitized solar cell
- 2006
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In: Physical Review Letters. - 1079-7114. ; 97:20
-
Journal article (peer-reviewed)abstract
- Using shaped laser pulses, we increase the yield of ultrafast electron injection from the sensitizer to TiO2 nanocrystals in the core part of a dye-sensitized solar cell. The temporal structure of the optimized excitation pulse is in clear correlation with nuclear oscillations in the impulsively excited dye molecule. From DFT structure optimization and normal mode analyses we identified the modes which are responsible for the oscillations. The best pulse shape suggests Impulsive Stimulated (anti-Stokes) Raman scattering as a key process of optimization.
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7. |
- Chen, Junsheng, et al.
(author)
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Enhanced Size Selection in Two-Photon Excitation for CsPbBr3 Perovskite Nanocrystals
- 2017
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In: Journal of Physical Chemistry Letters. - : American Chemical Society (ACS). - 1948-7185. ; 8:20, s. 5119-5124
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Journal article (peer-reviewed)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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8. |
- Christensson, Niklas, et al.
(author)
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Three-pulse photon echo peak shift in optically dense samples
- 2008
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In: Chemical Physics Letters. - : Elsevier BV. - 0009-2614. ; 457:1-3, s. 106-109
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Journal article (peer-reviewed)abstract
- We have investigated the dependence of the three-pulse photon echo peak-shift (3PEPS) signal on solute concentration and sample path length. The most prominent effect is an increase of the amplitude of the long decay component of the 3PEPS at high optical densities, but signal distortions are observed for all timescales in the experiments. The distortions of the peak shift signal are more severe for longer path lengths. These observations are assigned to pulse propagation effects. At low concentrations interference between the solute signal and the non-resonant solvent response severely distort the peak profiles at short population times.
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9. |
- Christensson, Niklas, et al.
(author)
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Weakly chirped pulses in frequency resolved coherent spectroscopy.
- 2010
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In: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 132:17, s. 1-174508
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Journal article (peer-reviewed)abstract
- The role of weakly chirped pulses (time bandwidth product, DeltanuDeltatau<0.61) on three-pulse photon echo signals has been systematically studied. Pulses with varying chirp were characterized with frequency resolved optical gating (FROG) and used to measure spectrally resolved three-pulse photon echoes of a dye in solution. The weakly chirped pulses give rise to markedly different echo signals for population times below approximately 100 fs. The chirped pulses can decrease or enhance spectral signatures of an excited state absorption transition in the echo signal. Furthermore, the observed dephasing dynamics depend on the phase of the electric fields. Simulations based on a three-level model and the electric fields retrieved from the FROG traces give a good agreement for photon echo experiments with both transform limited and chirped pulses. The simulations also allow for a numerical investigation of effects of chirp in two-dimensional spectroscopy. For a two-level system, the chirped pulses result in nonelliptical two-dimensional spectra that can erroneously be interpreted as spectral heterogeneity with frequency dependent dephasing dynamics. Furthermore, chirped pulses can give rise to "false" cross peaks when strong vibrational modes are involved in the system-bath interaction.
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10. |
- Corani, Alice, et al.
(author)
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Excited-State Proton-Transfer Processes of DHICA Resolved: From Sub-Picoseconds to Nanoseconds
- 2013
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In: The Journal of Physical Chemistry Letters. - : American Chemical Society (ACS). - 1948-7185. ; 4:9, s. 1383-1388
-
Journal article (peer-reviewed)abstract
- Excited-state proton transfer has been hypothesized as a mechanism for UV energy dissipation in eumelanin skin pigments. By using time resolved fluorescence spectroscopy, we show that the previously proposed, but unresolved, excited-state intramolecular proton transfer (ESIPT) of the eumelanin building block 5,6-dihydroxyindole-2-carboxylic acid (DHICA) occurs with a time constant of 300 fs in aqueous solution but completely stops in methanol. The previously disputed excited-state proton transfer involving the 5- or 6-OH groups of the DHICA anion is now found to occur from the 6-OH group to aqueous solvent with a rate constant of 4.0 x 10(8) s(-1).
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11. |
- De la Cadena, Alejandro, et al.
(author)
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Intermolecular exciton-exciton annihilation in phospholipid vesicles doped with [Ru(bpy)(2)dppz](2+)
- 2016
-
In: Chemical Physics Letters. - : Elsevier BV. - 0009-2614. ; 644, s. 56-61
-
Journal article (peer-reviewed)abstract
- The ultrafast photophysics of [Ru(bpy)(2)dppz](2+) (dppz = dipyrido[3,2-a:2',3'-c]-phenazine) embedded into the walls of phospholipid vesicles has been studied by femtosecond time-resolved pump-probe spectroscopy. While [Ru(bpy)(2)dppz](2+) has been studied intensively with respect to its intramolecular charge transfer processes, which are associated with the well known light-switch effect, this study focuses on intermolecular energy transfer processes taking place upon dense packing of the complexes into a phospholipid membrane composed of dipalmitoyl-t-a-phosphatidylglycerol, which can be thought of as a simplistic model of a cellular membrane. The data indicate additional quenching of excited [Ru(bpy)(2)dppz](2+) upon increasing the pump-pulse intensity. Hence, the observed photophysics, which is assigned to the presence of intermolecular exciton-exciton annihilation at high pump-intensities, might be related to the ultrafast photophysics of [Ru(bpy)(2)dppz](2+) when used as a chromophore to stain cells, an effect that may be taken into account during the employment of novel cellular markers based on Ru polypyridine complexes. (C) 2015 Elsevier B.V. All rights reserved.
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12. |
- De, Swati, et al.
(author)
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Exciton Dynamics in Alternating Polyfluorene/Fullerene Blends
- 2008
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In: Journal of Chemical Physics. - College Park, MD, United States : American Institute of Physics (AIP). - 0021-9606 .- 1089-7690. ; 350:1-3, s. 14-22
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Journal article (peer-reviewed)abstract
- Exciton dynamics in alternating copolymer/fullerene solar cell blends have been investigated using femtosecond transient absorption spectroscopy. The acceptor concentrations have been varied over a wide range. Experimental data, kinetic modeling and simulations, all indicate that the efficiency of exciton conversion to charges is 100% even at acceptor concentrations as low as 20 wt%. The reported dependence of solar cell efficiency on fullerene concentration may thus arise from other factors. However, there exists an acceptor concentration threshold (5 wt%) below which a substantial fraction of the excitations remain unquenched. The results, we believe are very relevant to optimization of performance efficiency by clever manipulation of morphology. We have also observed exciton–exciton energy transfer in these blends at low acceptor concentrations.
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13. |
- De, Swati, et al.
(author)
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Geminate charge recombination in alternating polyfluorene copolymer/fullerene blends
- 2007
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In: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; 129:27, s. 8466-8472
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Journal article (peer-reviewed)abstract
- By measuring excited state and charge dynamics in blends of an alternating polyfluorene copolymer and fullerene derivative over nine orders in time and two orders in light intensity, we have monitored the light-induced processes from ultrafast charge photogeneration to much slower decay of charges by recombination. We find that at low light intensities relevant to solar cell operation relatively fast (∼30 ns) geminate recombination is the dominating charge decay process, while nongeminate recombination has a negligible contribution. The conclusion of our work is that under solar illumination conditions geminate recombination of charges may be directly competing with efficient charge collection in polymer/fullerene solar cells. © 2007 American Chemical Society.
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14. |
- Dietzek, Benjamin, et al.
(author)
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Appearance of coherent artifact signals in femtosecond transient absorption spectroscopy in dependence on detector design
- 2007
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In: Laser Physics Letters. - : IOP Publishing. - 1612-2011 .- 1612-202X. ; 4:1, s. 38-43
-
Journal article (peer-reviewed)abstract
- The appearance of coherent artifact signals in transient absorption spectroscopy employing a spectrally integrated detection system is studied. The influence of the detection design on the shape of the observed signal is detailed and the experimentally very important case, in which the shape of the coherent artifact is strongly influenced by the presence of the sample itself, is considered - leading to the situation that the artifact signal cannot be accounted for by simple comparison of the kinetics obtained for the solvent only. Finally an estimate of the relative contribution of the artifact to the overall transient absorption change is presented facilitating the interpretation of short time transients in the presence of artifact contributions and allowing to estimate the excited state absorption cross-section for a known pump-intensity dependence of the artifact signal.
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15. |
- Dietzek, Benjamin, et al.
(author)
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Appearance of intramolecular high-frequency vibrations in two-dimensional, time-integrated three-pulse photon echo data
- 2007
-
In: Physical Chemistry Chemical Physics. - : Royal Society of Chemistry (RSC). - 1463-9084. ; 9:6, s. 701-710
-
Journal article (peer-reviewed)abstract
- An alternative experimental outline to measure homodyne detected three-pulse photon-echo data is presented. The novel experimental approach allowing for online monitoring and correction of experimental timing and stability is discussed in detail using the paradigm system of Nile blue in alcohol solution. It is shown that excellent signal-to-noise ratios together with high reproducibility of the data can be routinely achieved. We report in detail on the appearance of high-frequency intramolecular vibrations in the two-dimensional three-pulse photon-echo data and suggest that besides the conventionally discussed three-pulse photon-echo peak-shift the width of the integrated echo signal as a function of population time contains identical and easily accessible information on high-frequency intramolecular vibrations. A comparison of experimental data with theoretical modeling is performed showing that the observed echo-width oscillations are in line with predictions of the Brownian oscillator model.
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16. |
- Dietzek, Benjamin, et al.
(author)
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Control of a chemical reaction far from the Franck-Condon point by single-pulse resonant and non-resonant light-matter interaction.
- 2007
-
In: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 1520-5126 .- 0002-7863. ; 129:43, s. 13014-13021
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Journal article (peer-reviewed)abstract
- Using optimal control as a spectroscopic tool we decipher the details of the molecular dynamics of the essential multidimensional excited-state photoisomerization - a fundamental chemical reaction of key importance in biology. Two distinct nuclear motions are identified in addition to the overall bond-twisting motion: Initially, the reaction is dominated by motion perpendicular to the torsion coordinate. At later times, a second optically active vibration drives the system along the reaction path to the bottom of the excited-state potential. The time scales of the wavepacket motion on a different part of the excited-state potential are detailed by pump-shaped dump optimal control. This technique offers new means to control a chemical reaction far from the Franck-Condon point of absorption and to map details of excited-state reaction pathways revealing unique insights into the underlying reaction mechanism.
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17. |
- Dietzek, Benjamin, et al.
(author)
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Experimental observation of different-order components of a vibrational wave packet in a bulk dielectric using high-order Raman scattering
- 2007
-
In: Physical Review Letters. - 1079-7114. ; 98:18
-
Journal article (peer-reviewed)abstract
- We use high-order Raman scattering in a bulk dielectric to characterize coherent dynamics with precision typical for gas phase experiments. The experimental pump-probe approach allows for the simultaneous observation and separation in space and time of the individual contributions of different-order Raman processes to a coherent wave packet without relying on phase-matching conditions and within the same experimental geometry. We propose a novel technique to discriminate between stimulated excitation of vibronic levels in the impulsive and intermediate excitation regimes, futhermore allowing us to distinguish between different pathways contributing to the same fifth-order Raman processes.
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18. |
- Dietzek, Benjamin, et al.
(author)
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Mechanisms of molecular response in the optimal control of photoisomerization
- 2006
-
In: Physical Review Letters. - 1079-7114. ; 97:25
-
Journal article (peer-reviewed)abstract
- We report on adaptive feedback control of photoinduced barrierless isomerization of 1,1'-diethyl-2,2'-cyanine in solution. We compare the effect of different fitness parameters and show that optimal control of the absolute yield of isomerization (photoisomer concentration versus excitation photons) can be achieved, while the relative isomerization yield (photoisomer concentration versus number of relaxed excited-state molecules) is unaffected by adaptive feedback control. The temporal structure of the optimized excitation pulses allows one to draw clear mechanistic conclusions showing the critical importance of coherent nuclear motion for the control of isomerization.
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19. |
- Dietzek, Benjamin, et al.
(author)
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Optimal control of peridinin excited-state dynamics
- 2010
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In: Chemical Physics. - : Elsevier BV. - 0301-0104. ; 373:1-2, s. 129-136
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Journal article (peer-reviewed)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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20. |
- Dietzek, Benjamin, et al.
(author)
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Protochlorophyllide a: A Comprehensive Photophysical Picture
- 2009
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In: ChemPhysChem. - : Wiley. - 1439-7641 .- 1439-4235. ; 10:1, s. 144-150
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Journal article (peer-reviewed)abstract
- The photochemistry of protochlorophyllide a, a precursor in the biosynthesis of chlorophyll and substrate of the light regulated enzyme protochlorophyllide oxidoreductase, is investigated by pump-probe spectroscopy. Upon excitation into the lowest lying Q-band the light induced changes ore recorded over a wide range of probe wavelengths in the visible and near-IR region between 500 and 1000 nm. Following excitation, an initial ultrafast 450 Is process is observed related to the motion out of the Franck-Condon region on the excited state surface; thus directly unraveling previous suggestions based on time-resolved fluorescence measurements (ChemPhysChem 2006, 7, 1727-1733). Furthermore, the data reveals a previously concealed photointermediate, whose formation on a nanosecond timescale matches the overall fluorescence decay and is assigned to a triplet state. The implications of this finding with respect to the photochemistry of NADPH.-protochlorophyllide oxidoreductase (POR) ore discussed.
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21. |
- Dietzek, Benjamin, et al.
(author)
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Tracking ultrafast excited-state bond-twisting motion in solution close to the Franck-Condon point
- 2007
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In: The Journal of Physical Chemistry Part B. - : American Chemical Society (ACS). - 1520-5207 .- 1520-6106. ; 111:21, s. 6034-6041
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Journal article (peer-reviewed)abstract
- Applying optimal control to photoinduced trans-cis isomerization in condensed phase, the dynamics of bond-twisting motion of 1,1'-diethyl-4,4'-cyanine in methanol and propanol is revealed. The shape of the optimized pulse resulting from minimization of the photoisomer formation can be directly related to the initial excited-state dynamics in close proximity to the Franck-Condon point. The solvent viscosity-dependent ultrafast wavepacket motion is reflected in the prominent down-chirp of the optimized pulses and reveals a detailed picture of the control mechanism: The reduction of the isomer production is achieved by most efficient dumping of excited population back to the trans ground state. In the higher-viscosity solvent, propanol, wavelength-dependent oscillatory features are superimposed to the overall chirp structure pointing to the importance of excited-state vibrational coherences for the dumping process.
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22. |
- Dietzek, Benjamin, et al.
(author)
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Ultrafast excited-state isomerization dynamics of 1,1 '-diethyl-2,2 '-cyanine studied by four-wave mixing spectroscopy
- 2007
-
In: The Journal of Physical Chemistry Part B. - : American Chemical Society (ACS). - 1520-5207 .- 1520-6106. ; 111:19, s. 5396-5404
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Journal article (peer-reviewed)abstract
- Excited-state dynamics and solvent-solute interactions of 1,1'-diethyl-2,2'-cyanine iodine (1122C) in alcoholic solutions are investigated using time-integrated three-pulse photon-echo spectroscopy. 1122C serves as a model compound for ultrafast photoinduced isomerizationa key process in the light reception of plants, bacteria, and human vision. The photoreaction in 1122C is interrogated in dependence on solvent and excitation wavelength. The wavelength-dependent three-pulse photon-echo peak shift indicates strong alterations of the reaction pathways and points to the existence of a direct internal conversion channel in close proximity to the Franck-Condon point of absorption. The solvent-dependent S-1-S-0 internal conversion time does not follow conventional sheared viscosity dependence, suggesting that the solvent local friction has to be considered to account for the observed isomerization kinetics. The concerted discussion of transient grating and three-pulse photon-echo peak-shift data allows us to derive a complete picture of the solvent-solute interaction-controlled photoreaction. The results obtained are related to other work on reactive systems and are discussed in the framework of multilevel response functions.
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23. |
- El Nahhas, Amal, et al.
(author)
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Photochemistry of Pheomelanin Building Blocks and Model Chromophores: Excited-State Intra- and Intermolecular Proton Transfer
- 2014
-
In: The Journal of Physical Chemistry Letters. - : American Chemical Society (ACS). - 1948-7185. ; 5:12, s. 2094-2100
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Journal article (peer-reviewed)abstract
- Pheomelanins, the epidermal pigments of red-haired people responsible for their enhanced UV susceptibility, contain 1,4-benzothiazines and 1,3-benzothiazole as main structural components. Despite the major role played in pheomelanin phototoxicity, the photoreactivity of these species has so far remained unexplored. Static and time-resolved fluorescence spectroscopy was used to identify excited-state reactions of the two main pheomelanin benzothiazole building blocks, namely, the 6-(2-amino-2-carboxyethyl)-4-hydroxy-1,3-benzothiazole (BT) and the 2-carboxy derivative (BTCA) together with model chromophores lacking some of the ionizable functions. The results show that in aqueous buffer solution the OH at 4-position and the benzothiazole nitrogen atom control the photochemistry of both BT and BTCA via excited-state proton transfer to solvent (ESPT) and excited-state intramolecular proton transfer (ESIPT), while the amino acidic groups of the alanyl chain have a minor influence on the photochemistry. The ESPT and ESIPT produce several different excited-state ionic species with lifetimes ranging from similar to 100 ps to similar to 3 ns.
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24. |
- Ghanem, Raed, et al.
(author)
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Light-driven tyrosine radical formation in a ruthenium-tyrosine complex attached to nanoparticle TiO2
- 2002
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In: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 41:24, s. 6258-6266
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Journal article (peer-reviewed)abstract
- We demonstrate a possibility of multistep electron transfer in a supramolecular complex adsorbed on the surface of nanocrystalline TiO2. The complex mimics the function of the tyrosinez and chlorophyll unit P-680 in natural photosystem II (PSII). A ruthenium(II) tris(bipyridyl) complex covalently linked to a L-tyrosine ethyl ester through an amide bond was attached to the surface of nanocrystalline TiO2 via carboxylic acid groups linked to the bpy ligands. Synthesis and characterization of this complex are described. Excitation (450 nm) of the complex promotes an electron to a metal-to-ligand charge-transfer (MLCT) excited state, from which the electron is injected into TiO2. The photogeneration of Ru(III) is followed by an intramolecular electron transfer from tyrosine to Ru(III), regenerating the photosensitizer Ru(II) and forming the tyrosyl radical. The tyrosyl radical is formed in less than 5 us with a yield of 15%. This rather low yield is a result of a fast back electron transfer reaction from the nanocrystalline TiO2 to the photogenerated Ru(III).
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25. |
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