The neutralization reaction between an acid and a base in water, triggered after optical excitation, was studied by femtosecond vibrational spectroscopy. Bimodal dynamics were observed. In hydrogen-bonded acid-base complexes, the proton transfer proceeds extremely fast (within 150 femtoseconds). In encounter pairs formed by diffusion of uncomplexed photoacid and base molecules, the reaction upon contact was an order of magnitude slower, in agreement with earlier reported values. These results call for a refinement of the traditional Eigen-Weller picture of acid-base reactions: A three-stage model is introduced to account for all observed dynamics.

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We investigate one of the fundamental reactions in solutions, the neutralization of an acid by a base. We use a photoacid, 8-hydroxy-1,3,6-trisulfonate-pyrene (HPTS; pyranine), which upon photoexcitation reacts with acetate under transfer of a deuteron (solvent: deuterated water). We analyze in detail the resulting bimodal reaction dynamics between the photoacid and the base, the first report on which was recently published. We have ascribed the bimodal proton-transfer dynamics to contributions from preformed hydrogen bonding complexes and from initially uncomplexed acid and base. We report on the observation of an additional (6 ps)(-1) contribution to the reaction rate constant. As before, we analyze the slower part of the reaction within the framework of the diffusion model and the fastest part by a static, sub-150 fs reaction rate. Adding the second static term considerably improves the overall modeling of the experimental results. It also allows to connect experimentally the diffusion controlled bimolecular reaction models as defined by Eigen-Weller and by Collins-Kimball. Our findings are in agreement with a three-stage mechanism for liquid phase intermolecular proton transfer: mutual diffusion of acid and base to form a "loose" encounter complex, followed by reorganization of the solvent shells and by "tightening" of the acid-base encounter complex. These rearrangements last a few picoseconds and enable a prompt proton transfer along the reaction coordinate, which occurs faster than our time resolution of 150 fs. Alternative models for the explanation of the slower "on-contact" reaction time of the loose encounter complex in terms of proton transmission through a von Grotthuss mechanism are also discussed.

We report on the first demonstration of femtosecond x-ray absorption spectroscopy, made uniquely possible by the use of broadly tunable bending-magnet radiation from "laser-sliced" electron bunches within a synchrotron storage ring. We measure the femtosecond electronic rearrangements that occur during the photoinduced insulator-metal phase transition in VO2. Symmetry- and element-specific x-ray absorption from V2p and O1s core levels (near 500 eV) separately measures the filling dynamics of differently hybridized V3d-O2p electronic bands near the Fermi level.

Photo-excitation can drive strongly correlated electron insulators into competing conducting phases, resulting in giant and ultrafast changes of their electronic and magnetic properties. The underlying non-equilibrium dynamics involve many degrees of freedom at once, whereby sufficiently short optical pulses can trigger the corresponding collective modes of the solid along temporally coherent pathways. The characteristic frequencies of these modes range between the few GHz of acoustic vibrations to the tens or even hundreds of THz for purely electronic excitations. Virtually all experiments so far have used 100 fs or longer pulses, detecting only comparatively slow lattice dynamics. Here, we use sub-10-fs optical pulses to study the photo-induced insulator-metal transition in the magnetoresistive manganite Pr(0.7)Ca(0.3)MnO(3). At room temperature, we find that the time-dependent pathway towards the metallic phase is accompanied by coherent 31 THz oscillations of the optical reflectivity, significantly faster than all lattice vibrations. These high-frequency oscillations are suggestive of coherent orbital waves, crystal-field excitations triggered here by impulsive stimulated Raman scattering. Orbital waves are likely to be initially localized to the small polarons of this room-temperature manganite, coupling to other degrees of freedom at longer times, as photo-domains coalesce into a metallic phase.

We present a femtosecond UV-mid-IR pump-probe study of the photochemical ring-opening reaction of the spiropyran 1',3',3',-trimethylspiro-[-2H-1-benzopyran-2,2'-indoline] (also known as BIPS) in tetrachloroethene, using 70 fs UV excitation pulses and probing with 100 fs mid-IR pulses. The time evolution of the transient IR absorption spectrum was monitored over the first 100 ps after UV excitation. We conclude that the merocyanine product is formed with a 28 ps time constant, contrasting with a 0.9 ps time constant obtained in previous investigations where the rise of absorption bands at visible wavelengths were associated with product formation. We deduce from the observed strong recovery of the spiropyran IR absorption bleaches that, in tetrachloroethene, the main decay channel for the S(1) excited state of the spiropyran BIPS, is internal conversion to the spiropyran S(0) state with a quantum yield of > or = 0.9. This puts an upper limit of 0.1 to the quantum yield of the photochemical ring-opening reaction.

We report the first time-resolved site-specific mid-infrared study of the photo-induced excited state hydrogen transfer reaction in 2-(2'-hydroxyphenyl)benzothiazole (HBT) with 130 fs time resolution. The transient absorption of the C=O stretching band marking the keto*-S1-state appears delayed on a time scale of 30-50 fs after electronic excitation to the enol*-S1-state. Its line center subsequently shifts up by about 3-5 cm(-1) after excitation, depending on the excitation wavelength tuned between 315 and 349 nm. This effect is attributed to intramolecular vibrational energy redistribution (IVR) and vibrational energy relaxation (VER) processes. We observe for the first time the coherent effects of anharmonic coupling of low frequency modes (approximately 60 cm(-1), approximately 120 cm(-1)), on the C=O mode marking the product state. We ascribe the 120 cm(-1) mode to a Raman-active in-plane deformation mode that is coherently excited by the UV-pump pulse. We tentatively explain the coherent excitation of the infrared active 60 cm(-1) out-of-plane deformation mode by nonradiative processes within the excited enol state after electronic excitation.

We study the ultrafast insulator-to-metal transition in nanoparticles of VO2, obtained by ion implantation and self-assembly in silica. The nonmagnetic, strongly correlated compound VO2 undergoes a reversible phase transition, which can be photoinduced on an ultrafast time scale. In the nanoparticles, prompt formation of the metallic state results in the appearance of surface-plasmon resonance. We achieve large, ultrafast enhancement of optical absorption in the near-infrared spectral region that encompasses the wavelength range for optical-fiber communications. One can further tailor the response of the nanoparticles by controlling their shape.