Project description:Metalloporphyrins with open d-shell ions can drive biochemical energy cycles. However, their utilization in photoconversion is hampered by rapid deactivation. Mapping the relaxation pathways is essential for elaborating strategies that can favorably alter the charge dynamics through chemical design and photoexcitation conditions. Here, we combine transient optical absorption spectroscopy and transient X-ray emission spectroscopy with femtosecond resolution to probe directly the coupled electronic and spin dynamics within a photoexcited nickel porphyrin in solution. Measurements and calculations reveal that a state with charge-transfer character mediates the formation of the thermalized excited state, thereby advancing the description of the photocycle for this important representative molecule. More generally, establishing that intramolecular charge-transfer steps play a role in the photoinduced dynamics of metalloporphyrins with open d-shell sets a conceptual ground for their development as building blocks capable of boosting nonadiabatic photoconversion in functional architectures through "hot" charge transfer down to the attosecond time scale.
Project description:The ultrafast dynamics of excited states in cerium oxide are investigated to access the early moments of polaron formation, which can influence the photocatalytic functionality of the material. UV transient absorbance spectra of photoexcited CeO2 exhibit a bleaching of the band edge absorbance induced by the pump and a photoinduced absorbance feature assigned to Ce 4f → Ce 5d transitions. A blue shift of the spectral response of the photoinduced absorbance signal in the first picosecond after the pump excitation is attributed to the dynamical formation of small polarons with a characteristic time of 330 fs. A further important result of our work is that the combined use of steady-state and ultrafast transient absorption allows us to propose a revised value for the optical gap for ceria (Eog = 4 eV), significantly larger than usually reported.
Project description:The fundamental mechanisms of charge migration in DNA are pertinent for current developments in molecular electronics and electrochemistry-based chip technology. The energetic control of hole (positive ion) multistep hopping transport in DNA proceeds via the guanine, the nucleobase with the lowest oxidation potential. Chemical yield data for the relative reactivity of the guanine cations and of charge trapping by a triple guanine unit in one of the strands quantify the hopping, trapping, and chemical kinetic parameters. The hole-hopping rate for superexchange-mediated interactions via two intervening AT base pairs is estimated to be 10(9) s(-1) at 300 K. We infer that the maximal distance for hole hopping in the duplex with the guanine separated by a single AT base pair is 300 +/- 70 A. Although we encounter constraints for hole transport in DNA emerging from the number of the mediating AT base pairs, electron transport is expected to be nearly sequence independent because of the similarity of the reduction potentials of the thymine and of the cytosine.
Project description:Base stacking in DNA is related to long-living excited states whose molecular nature is still under debate. To elucidate the molecular background we study well-defined oligonucleotides with natural bases, which allow selective UV excitation of one single base in the strand. IR probing in the picosecond regime enables us to dissect the contribution of different single bases to the excited state. All investigated oligonucleotides show long-living states on the 100-ps time scale, which are not observable in a mixture of single bases. The fraction of these states is well correlated with the stacking probabilities and reaches values up to 0.4. The long-living states show characteristic absorbance bands that can be assigned to charge-transfer states by comparing them to marker bands of radical cation and anion spectra. The charge separation is directed by the redox potential of the involved bases and thus controlled by the sequence. The spatial dimension of this charge separation was investigated in longer oligonucleotides, where bridging sequences separate the excited base from a sensor base with a characteristic marker band. After excitation we observe a bleach of all involved bases. The contribution of the sensor base is observable even if the bridge is composed of several bases. This result can be explained by a charge delocalization along a well-stacked domain in the strand. The presence of charged radicals in DNA strands after light absorption may cause reactions--oxidative or reductive damage--currently not considered in DNA photochemistry.
Project description:Copper tungstate (CuWO4) is an important semiconductor with a sophisticated and debatable electronic structure that has a direct impact on its chemistry. Using the PAL-XFEL source, we study the electronic dynamics of photoexcited CuWO4. The Cu L3 X-ray absorption spectrum shifts to lower energy upon photoexcitation, which implies that the photoexcitation process from the oxygen valence band to the tungsten conduction band effectively increases the charge density on the Cu atoms. The decay time of this spectral change is 400 fs indicating that the increased charge density exists only for a very short time and relaxes electronically. The initial increased charge density gives rise to a structural change on a time scale longer than 200 ps.
Project description:Magnetic materials play a vital role in energy-efficient data storage technologies, combining very fast switching with long-term retention of information. However, it has been shown that, at very short time scales, magnetisation dynamics become chaotic due to internal instabilities, resulting in incoherent spin-wave excitations that ultimately destroy magnetic ordering. Here, contrary to expectations, we show that such chaos gives rise to a periodic pattern of reversed magnetic domains, with a feature size far smaller than the spatial extent of the excitation. We explain this pattern as a result of phase-synchronisation of magnon-polaron quasiparticles, driven by strong coupling of magnetic and elastic modes. Our results reveal not only the peculiar formation and evolution of magnon-polarons at short time-scales, but also present an alternative mechanism of magnetisation reversal driven by coherent packets of short-wavelength magnetoelastic waves.
Project description:We implemented spatial mapping of charge carrier density in the channel of a conventional polymer Field-Effect Transistor (FET) by mid-infrared Charge Modulation Spectroscopy (CMS). CMS spectra are recorded with a high sensitivity confocal Fourier Transform Infra-Red (FTIR) microscope by probing electroinduced Infra-Red Active Vibrational (IRAV) modes and low-energy polaron bands in the spectral region 680-4000 cm(-1). Thanks to the high specificity and strong oscillator strength of these modes, charge-induced reflectance measurements allow quantitative estimation of charge carrier densities within the FET channel, without the need for amplitude or phase modulation. This is illustrated by identifying the contribution of intrinsic and electrostatically induced polarons to conduction, and by mapping the polaron spatial distribution in a P3HT (Poly(3-hexylthiophene-2,5-diyl)) FET channel under different drain-source bias conditions. This work demonstrates the potential of mid-infrared charge modulation microscopy to characterize carrier injection and transport in semiconducting polymer materials.
Project description:The photoinduced ultrafast coherent inter-chromophore energy redistribution in a triarylamine trimer is explored using nonadiabatic excited state molecular dynamics followed by simulations of X-ray Raman signals. The nitrogencentered system ensures strong interchromophore interactions and, thus, the presence of coherences. Nevertheless, the multitude of non-deterministic photoinduced pathways during the ultrafast inter-branch migration of the excitation results in random confinement on some branches and, therefore, spatial exciton scrambling and loss of phase information at long times. We show that the vibronic coherence dynamics evolving into the incoherent scrambling mechanism on ultrafast 50 fs timescale, is accurately probed by the TRUECARS X-ray stimulated Raman signal. In combination with previous results, where the technique has revealed long-lived coherences in a rigid heterodimer, the signal is most valuable for detecting ultrafast molecular coherences or their absence. We demonstrate that X-ray Raman spectroscopy is a useful tool in the chemical design of functional molecular building blocks.
Project description:Since the early days of quantum mechanics, it has been known that electrons behave simultaneously as particles and waves, and now quantum electronic devices can harness this duality. When devices are shrunk to the molecular scale, it is unclear under what conditions does electron transmission remain phase-coherent, as molecules are usually treated as either scattering or redox centers, without considering the wave-particle duality of the charge carrier. Here, we demonstrate that electron transmission remains phase-coherent in molecular porphyrin nanoribbons connected to graphene electrodes. The devices act as graphene Fabry-Pérot interferometers and allow for direct probing of the transport mechanisms throughout several regimes. Through electrostatic gating, we observe electronic interference fringes in transmission that are strongly correlated to molecular conductance across multiple oxidation states. These results demonstrate a platform for the use of interferometric effects in single-molecule junctions, opening up new avenues for studying quantum coherence in molecular electronic and spintronic devices.
Project description:The interaction of electrons with the lattice in metals can lead to reduction of their kinetic energy to the point where they may form heavy, dressed quasiparticles-polarons. Unfortunately, polaronic lattice distortions are difficult to distinguish from more conventional charge- and spin-ordering phenomena at low temperatures. Here we present a study of local symmetry breaking of the lattice structure on the picosecond timescale in the prototype layered dichalcogenide Mott insulator 1T-TaS2 using X-ray pair-distribution function measurements. We clearly identify symmetry-breaking polaronic lattice distortions at temperatures well above the ordered phases, and record the evolution of broken symmetry states from 915 K to 15 K. The data imply that charge ordering is driven by polaron crystallization into a Wigner crystal-like state, rather than Fermi surface nesting or conventional electron-phonon coupling. At intermediate temperatures the local lattice distortions are found to be consistent with a quantum spin liquid state.