21 research outputs found
Time resolved X ray absorption spectroscopy of infrared laser induced temperature jumps in liquid water
A time resolved X ray absorption study of the structural dynamics of liquid water on a picosecond timescale is presented. We apply femtosecond midinfrared pulses to resonantly excite the intramolecular O H stretching band of liquid water and monitor the transient response in the oxygen K edge absorption spectrum with picosecond X ray pulses. In this way, structural changes in the hydrogen bond network of liquid water upon an ultrafast temperature jump of approximately 20 K are investigated. The changes of the X ray absorption as induced by such a temperature jump are about 3.2 . This demonstrates that our method serves as a sensitive probe of transient structural changes in liquid water and that combined infrared laser synchrotron experiments with substantially shorter X ray pulses, such as generated with a femtosecond slicing scheme, are possibl
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Competition between excited state proton and OH- transport via a short water wire: Solvent effects open the gate
We investigate the acid-base proton exchange reaction in a microsolvated bifunctional chromophore by means of quantum chemical calculations. The UV/vis spectroscopy shows that equilibrium of the keto-and enol-forms in the electronic ground state is shifted to the keto conformation in the excited state. A previously unknown mechanism involving a hydroxide ion transport along a short water wire is characterized energetically, which turns out to be competitive with the commonly assumed proton transport. Both mechanisms are shown to have a concerted character, as opposed to a step-wise mechanism. The alternative mechanism of a hydrogen atom transport is critically examined, and evidence for strong solvent dependence is presented. Specifically, we observe electrostatic destabilization of the corresponding πσ* state by the aqueous solvent. As a consequence, no conical intersections are found along the reaction pathway
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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
Aqueous Solvation of Ammonia and Ammonium Probing Hydrogen Bond Motifs with FT IR and Soft X ray Spectroscopy
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Ultrafast IR pump-probe and 2D-IR photon echo spectroscopy of adenosine-thymidine base pairs
We characterize diagonal and off-diagonal anharmonicities of N-H stretching vibrations in adenosine and thymidine monomers and in A•T-base pairs in chloroform solution, showing the important role of coupling between vibrationally excited N-H stretching states
From local covalent bonding to extended electric field interactions in proton hydration
Seemingly simple yet surprisingly difficult to probe, excess protons in water constitute complex quantum objects with strong interactions with the extended and dynamically changing hydrogen-bonding network of the liquid. Proton hydration plays pivotal roles in energy transport in hydrogen fuel cells and signal transduction in transmembrane proteins. While geometries and stoichiometry have been widely addressed in both experiment and theory, the electronic structure of these specific hydrated proton complexes has remained elusive. Here we show, layer by layer, how utilizing novel flatjet technology for accurate x-ray spectroscopic measurements and combining infrared spectral analysis and calculations, we find orbital-specific markers that distinguish two main electronic-structure effects: Local orbital interactions determine covalent bonding between the proton and neigbouring water molecules, while orbital-energy shifts measure the strength of the extended electric field of the proton
Von lokalen kovalenten Bindungen zu langreichweitigen elektrischen Wechselwirkungen der Protonenhydratation
Ultrafast vibrational dynamics of water confined in phospholipid reverse micelles
We study the ultrafast dynamics of OH stretching and bending vibrations of water inside dioleoylphosphatidylcholine (DOPC) reverse micelles in a wide range of hydration. A strong hydration level dependence for the spectral diffusion rates is found and explained by the distinctly different environment for single water molecules bound to the anionic phosphate group. We show that the energy relaxation pathway of the OH stretching vibration at low hydration level involves the OH bending