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L-edge XANES analysis of photoexcited metal complexes in solution

Ultrafast X-ray absorption spectroscopy is a powerful tool to observe electronic and geometric structures of short-lived reaction intermediates. The ab initiofeff9 code is applied to simulate the Pt L3-edge XANES spectrum of the photocatalytic diplatinum molecule [Pt2(P2O5H2)4]4− and the photo-induced changes that occur therein. The spectra are interpreted within a XAFS-like scattering theoretical

Retrieving photochemically active structures by time-resolved EXAFS spectroscopy

Describing the nature and structure of molecular excited states is important in order to understand their chemical reactivity and role as intermediates in photochemical reactions. The recent implementation of X-ray absorption spectroscopy in the ultrafast time domain allows studying the electronic and structural dynamics of photochemically active molecules in solutions. In this work we present the

Time-resolved X-ray absorption spectroscopy : Watching atoms dance

The introduction of pump-probe techniques to the field of X-ray absorption spectroscopy (XAS) has allowed the monitoring of both structural and electronic dynamics of disordered systems in the condensed phase with unprecedented accuracy, both in time and in space. We present results on the electronically excited high-spin state structure of an Fe(II) molecular species, [Fe II(bpy)3]2+, in aqueous

Structural determination of a photoehemieally active diplatinum molecule by time-resolved EXAFS spectroscopy

Metallica: A large contraction of the Pt-Pt bond in the triplet excited state of the photoreactive [Pt2(P2O5H 2)4]4- ion is determined by time-resolved X-ray absorption spectroscopy (see picture). The strengthening of the Pt-Pt interaction is accompanied by a weakening of the ligand coordination bonds, resulting in an elongation of the platinum-ligand bond that is determined for the first time.

Structural analysis of ultrafast extended x-ray absorption fine structure with subpicometer spatial resolution : Application to spin crossover complexes

We present a novel analysis of time-resolved extended x-ray absorption fine structure (EXAFS) spectra based on the fitting of the experimental transients obtained from optical pump/x-ray probe experiments. We apply it to the analysis of picosecond EXAFS data on aqueous [FeII (bpy)3] 2+, which undergoes a light induced conversion from its low-spin (LS) ground state to the short-lived (τ≈650 ps) exc

Femtosecond XANES study of the light-induced spin crossover dynamics in an iron(II) complex

X-ray absorption spectroscopy is a powerful probe of molecular structure, but it has previously been too slow to track the earliest dynamics after photoexcitation. We investigated the ultrafast formation of the lowest quintet state of aqueous iron(II) tris(bipyridine) upon excitation of the singlet metal-to-ligand-charge-transfer ( 1 MLCT) state by femtosecond optical pump/x-ray probe techniques

EXAFS structural determination of the Pt2(P2O 5H2)44- anion in solution

We present the first structural determination of the Pt2(P 2O5H2)44- anion in solution by analyzing the extended X-ray absorption fine structure (EXAFS) spectrum of the Pt LIII edge. The data could be fit with a simple model involving single and multiple scattering paths to near and far P-atoms, bridging O-atoms, and the other Pt-atom in the binuclear complex. A Pt-Pt distance of 2.876(28) Å and a

Ultrafast X-ray spectroscopy for structural dynamics studies in chemistry and biology

Time-resolved x-ray absorption fine structure (XAFS) spectroscopy with pico-second temporal resolution is a new method to observe electronic and geometric structures of short-lived reaction intermediates. It combines an intense femto-second laser source synchronized to the x-ray pulses delivered into the microXAS beamline of the Swiss Light Source (SLS). We present key experiments on charge transf

Ultrafast nonadiabatic dynamics of [FeII(bpy)3] 2+ in solution

The ultrafast relaxation of aqueous iron(II)-tris(bipyridine) upon excitation into the singlet metal-to-ligand charge-transfer band ( 1MLCT) has been characterized by femtosecond fluorescence up-conversion and transient absorption (TA) studies. The fluorescence experiment shows a very short-lived broad 1MLCT emission band at ∼600 nm, which decays in ≤20 fs, and a weak emission at ∼660 nm, which we

Light-induced spin crossover probed by ultrafast optical and X-ray spectroscopies

The photoinduced energy and structural relaxation of aqueous iron(II)-tris-bipyridine ([FeII(bpy)3]2+), upon excitation into its singlet metal-to-ligand charge transfer (1MLCT) band, and the population of its short-lived (≤0.6 ns) high-spin excited state have been characterized by combined ultrafast optical and X-ray spectroscopies. Polychromatic femtosecond fluorescence up-conversion reveals a ve

Capturing transient electronic and molecular structures in liquids by picosecond X-ray absorption spectroscopy

We describe an advanced setup for time-resolved x-ray absorption fine structure (XAFS) Spectroscopy with picosecond temporal resolution. It combines an intense femtosecond laser source synchronized to the x-ray pulses delivered into the microXAS beamline of the Swiss Light Source (SLS). The setup is applied to measure the short-lived high-spin geometric structure of photoexcited aqueous Fe(bpy) 3

Observation of the solvent shell reorganization around photoexcited atomic solutes by picosecond X-ray absorption spectroscopy

We report on the observation of the solvation shell rearrangement after abstraction of the electron from aqueous I - in a laser pump/X-ray probe experiment by recording the X-ray absorption L 1 - and L 3 -edge spectra, 50 ps after laser excitation. The L 1 -edge spectra clearly identify the I 0 neutral species after excitation and suggest a substantial amount of back-transfer of charge from the s

Structural determination of a short-lived excited iron(II) complex by picosecond X-ray absorption spectroscopy

Structural changes of the iron(II)-tris-bipyridine ([FeII(bpy)3]2+) complex induced by ultrashort pulse excitation and population of its short-lived (0.6ns) quintet high spin state have been detected by picosecond x-ray absorption spectroscopy. The structural relaxation from the high spin to the low spin state was followed over the entire lifetime of the excited state. A combined analysis of the x

Light-induced absorption and holographic recording in Pr:LINbO 3

With ultraviolet illumination, we have found a broad UV-induced absorption in the blue and some involvement of Pr ions in Pr:LiNbO 3 . Transient and stable absorption induced by UV illumination was analyzed at 457, 514, and 633 nm and could be explained by hole trap centers and iron ions. We also studied the effects of UV illumination and boundary conditions during holographic recording in the vi

Nonvolatile two-color holographic recording in Tm-doped near-stoichiometric LiNbO 3

We have observed ultraviolet-induced visible absorption and performed two-color holographic recording at green, red, and near-infrared light in thulium doped near-stoichiometric LiNbO 3 crystal. The diffraction efficiency and sensitivity of the recording process at all wavelengths are increased by ultraviolet gating light. Characteristics of recording in the visible are explained by a two-center

Change of optical band gap and magnetization with Mn concentration in Mn-doped AlN films

Mn-doped AlN films were prepared by magnetron reactive sputtering system. The preparation conditions were optimized to give pure single-phase AlMnN films. The films were deposited on quartz substrates. The single-phase films were obtained in argon-nitrogen pressure of 6 mTorr and a substrate temperature of 300 °C. The films typically had a thickness of 0.4 μm. The XRD pattern indicated a pure AlM

Optical spectroscopy of thulium-doped oxyfluoroborate glass

Optical spectroscopy of Tm3+-doped 59H3BO 3-20ZnO-20LiF-1Tm2O3 glass is presented. From the measured absorption spectra, radiative parameters were determined using the Judd-Ofelt (JO) theory. Excitation in the range of 750-800 nm resulted in a frequency up-converted emission at 453 nm (1D2 → 3F4). Excitation spectra and intensity dependence of the up-converted fluorescence have been investigated a

Large magnetic entropy change in a la0.8Ca0.2MnO 3 single crystal

A large magneto-caloric effect is reported in a La0.8Ca 0.2MnO3 single crystal. The magnetic entropy change (ΔSM) reaches ∼7.25 J/kg K for an applied field of 5 T, which is very practical for magnetic refrigeration applications. Satisfactory agreement between the theoretical calculations on ΔSM derived in the molecular field approximation and the experimental dependency has been found.