A liquid flatjet system for solution phase soft-x-ray spectroscopy

We present a liquid flatjet system for solution phase soft-x-ray spectroscopy. The flatjet set-up utilises the phenomenon of formation of stable liquid sheets upon collision of two identical laminar jets. Colliding the two single water jets, coming out of the nozzles with 50 μm orifices, under an impact angle of 48° leads to double sheet formation, of which the first sheet is 4.6 mm long and 1.0 mm wide. The liquid flatjet operates fully functional under vacuum conditions (<10(-3) mbar), allowing soft-x-ray spectroscopy of aqueous solutions in transmission mode. We analyse the liquid water flatjet thickness under atmospheric pressure using interferomeric or mid-infrared transmission measurements and under vacuum conditions by measuring the absorbance of the O K-edge of water in transmission, and comparing our results with previously published data obtained with standing cells with Si3N4 membrane windows. The thickness of the first liquid sheet is found to vary between 1.4-3 μm, depending on the transverse and longitudinal position in the liquid sheet. We observe that the derived thickness is of similar magnitude under 1 bar and under vacuum conditions. A catcher unit facilitates the recycling of the solutions, allowing measurements on small sample volumes (∼10 ml). We demonstrate the applicability of this approach by presenting measurements on the N K-edge of aqueous NH4 (+). Our results suggest the high potential of using liquid flatjets in steady-state and time-resolved studies in the soft-x-ray regime

Ultrafast proton coupled electron transfer (PCET) dynamics in 9-anthranol-aliphatic amine system

Femtosecond infrared absorption studies strongly suggest that photoexcited 9-anthranol takes part in an ultrafast electron transfer (ET) reaction in electron-donating triethylamine solvent, but that ultrafast proton coupled electron transfer (PCET) occurs in diethylamine solvent

Switching between Proton Vacancy and Excess Proton Transfer Pathways in the Reaction between 7-Hydroxyquinoline and Formate

Bifunctional or amphoteric photoacids simultaneously present donor (acidic) and acceptor (basic) properties making them useful tools to analyze proton transfer reactions. In protic solvents, the proton exchange between the acid and the base is controlled by the acidity or basicity strength and typically occurs on two different pathways known as protolysis and hydrolysis. We report here how the addition of a formate base will alter the relative importance of the possible reaction pathways of the bifunctional photoacid 7-hydroxyquinoline (7HQ), which has been recently understood to predominantly involve a hydroxide/methoxide transport mechanism between the basic proton-accepting quinoline nitrogen site toward the proton-donating OH group with a time constant of 360 ps in deuterated methanol (CD3OD). We follow the reaction dynamics by probing the IR-active marker modes of the different charged forms of photoexcited 7HQ, and of formic acid (HCOOD) in CD3OD solution. A comparison of the transient IR spectra as a function of formate concentration, and classical molecular dynamics simulations enables us to identify distinct contributions of “tight” (meaning “contact”) and “loose” (i.e., “solvent-separated”) 7HQ–formate reaction pairs in our data. Our results suggest that depending on the orientation of the OH group with respect to the quinoline aromatic ring system, the presence of the formate molecule in a proton relay pathway facilitates a net proton transfer from the proton-donating OH group of 7HQ-N* via the methanol/formate bridge toward the quinoline N site

Filamentary pulse self-compression: The impact of the cell windows

Self-compression of multi-millijoule laser pulses during filamentary propagation is usually explained by the interplay of self-focusing and defocusing effects, causing a substantial concentration of energy on the axis of the propagating optical pulse. Recently, it has been argued that cell windows may play a decisive role in the self-compression mechanism. As such windows have to be used for media other than air their presence is often unavoidable, yet they present a sudden non-adiabatic change in dispersion and nonlinearity that should lead to a destruction of the temporal and spatial integrity of the light bullets generated in the self-compression mechanism. We now experimentally prove that there is in fact a self-healing mechanism that helps to overcome the potentially destructive consequences of the cell windows. We show in two carefully conducted experiments that the cell window position decisively influences activation or inhibition of the self-healing mechanism. A comparison with a windowless cell shows that presence of this mechanism is an important prerequisite for the exploitation of self-compression effects in windowed cells filled with inert gases

Photoinduced Bimolecular Electron Transfer Investigated by Femtosecond Time-Resolved Infrared Spectroscopy

Ultrafast infrared transient absorption spectroscopy is used to study the photoinduced bimolecular electron transfer reaction between perylene in the first singlet excited state and 1,4-dicyanobenzene in acetonitrile and dichloromethane. Following vibrational marker modes on both donor and acceptor sides in real time provides direct insight into the structural dynamics during the reaction. A band narrowing on a time scale of a few tens of picoseconds observed on the antisymmetric CN stretching vibration of the dicyanobenzene radical anion indicates that a substantial part of the excess energy is channeled into vibrational modes of the product, despite the fact that the reaction is weakly exergonic. An additional narrowing of the same band on a time scale of several hundreds of picoseconds observed in acetonitrile only is interpreted as a signature of the dissociation of the geminate ion pairs into free ions

Direct Femtosecond Observation of Tight and Loose Ion Pairs upon Photoinduced Bimolecular Electron Transfer

Polarisationsempfindliche ultraschnelle Infrarotmessungen des photoinduzierten Elektronentransfers in Donor-Akzeptor-Paaren in polarem Acetonitril können individuelle Beiträge locker und fest gebundener Ionenpaare detektieren. Die hoch anisotropen Signale der zweiten verdeutlichen, dass die gegenseitige Orientierung der Reaktionspartner wichtig ist (siehe Bild), d. h., bisherige theoretische Modelle, die nur die Abstände zwischen sphärischen Spezies berücksichtigen, müssen verfeinert werden

Highly efficient soft x-ray spectrometer for transient absorption spectroscopy with broadband table-top high harmonic sources

We present a novel soft x-ray spectrometer for ultrafast absorption spectroscopy utilizing table-top femtosecond high-order harmonic sources. Where most commercially available spectrometers rely on spherical variable line space gratings with a typical efficiency on the order of 3% in the first diffractive order, this spectrometer, based on a Hettrick–Underwood design, includes a reflective zone plate as a dispersive element. An improved efficiency of 12% at the N K-edge is achieved, accompanied by a resolving power of 890. The high performance of the soft x-ray spectrometer is further demonstrated by comparing nitrogen K-edge absorption spectra from calcium nitrate in aqueous solution obtained with our high-order harmonic source to previous measurements performed at the electron storage ring facility BESSY II

ULTRAFAST ELECTRONIC FLUCTUATION AND SOLVATION IN LIQUIDS

Solvation and optical dephasing of electronic transitions in molecular liquids are studied over a large range of time scales. It is shown that these optical effects, which are due to coupling of the electronic degrees of freedom with the nuclear motion in the liquid, are closely connected. The rapidly changing nuclear configurations are modelled by Brownian motion in harmonic potential wells. From photon echo decays, that occur on a timescale of 20 femtoseconds or faster, optical properties such as the chirped four-wave mixing response (timescale 50-200 fs) and the absorption and emission spectra (steady state) can be calculated in a straightforward manner. The magnitude of the Stokes shift is also predicted accurately. The physical significance of this approach to optical dynamics in liquids is discussed in the context of molecular dynamics simulations

Ultrafast forward and backward electron transfer dynamics of coumarin 337 in hydrogen-bonded anilines as studied with femtosecond UV-pump/IR-probe spectroscopy

Femtosecond infrared spectroscopy is used to study both forward and backward electron transfer (ET) dynamics between coumarin 337 (C337) and the aromatic amine solvents aniline (AN), N-methylaniline (MAN), and N,N-dimethylaniline (DMAN), where all the aniline solvents can donate an electron but only AN and MAN can form hydrogen bonds with C337. The formation of a hydrogen bond with AN and MAN is confirmed with steady state FT-IR spectroscopy, where the C═O stretching vibration is a direct marker mode for hydrogen bond formation. Transient IR absorption measurements in all solvents show an absorption band at 2166 cm−1, which has been attributed to the C≡N stretching vibration of the C337 radical anion formed after ET. Forward electron transfer dynamics is found to be biexponential with time constants τET1 = 500 fs, τET2 = 7 ps in all solvents. Despite the presence of hydrogen bonds of C337 with the solvents AN and MAN, no effect has been found on the forward electron transfer step. Because of the absence of an H/D isotope effect on the forward electron transfer reaction of C337 in AN, hydrogen bonds are understood to play a minor role in mediating electron transfer. In contrast, direct π-orbital overlap between C337 and the aromatic amine solvents causes ultrafast forward electron transfer dynamics. Backward electron transfer dynamics, in contrast, is dependent on the solvent used. Standard Marcus theory explains the observed backward electron transfer rates