Femtosecond Dynamics of Excited-State Evolution in

Time-resolved absorption spectroscopy on the femtosecond time scale has been used to monitor the earliest events associated with excited-state relaxation in tris-(2,2'-bipyridine)ruthenium(II). The data reveal dynamics associated with the temporal evolution of the Franck-Condon state to the lowest energy excited state of this molecule. The process is essentially complete in approximately 300 femtoseconds after the initial excitation. This result is discussed with regard to reformulating long-held notions about excited-state relaxation, as well as its implication for the importance of non-equilibrium excited-state processes in understanding and designing molecular-based electron transfer, artificial photosynthetic, and photovoltaic assemblies in which compounds of this class are currently playing a key role.     

Generation of femtosecond pulses of synchrotron radiation

Femtosecond synchrotron pulses were generated directly from an electron storage ring. An ultrashort laser pulse was used to modulate the energy of electrons within a 100-femtosecond slice of the stored 30-picosecond electron bunch. The energy-modulated electrons were spatially separated from the long bunch and used to generate approximately 300-femtosecond synchrotron pulses at a bend-magnet beamline, with a spectral range from infrared to x-ray wavelengths. The same technique can be used to generate approximately 100-femtosecond x-ray pulses of substantially higher flux and brightness with an undulator. Such synchrotron-based femtosecond x-ray sources offer the possibility of applying x-ray techniques on an ultrafast time scale to investigate structural dynamics in condensed matter.     

Ultrafast bond softening in bismuth: mapping a solid's interatomic potential with X-rays

Intense femtosecond laser excitation can produce transient states of matter that would otherwise be inaccessible to laboratory investigation. At high excitation densities, the interatomic forces that bind solids and determine many of their properties can be substantially altered. Here, we present the detailed mapping of the carrier density-dependent interatomic potential of bismuth approaching a solid-solid phase transition. Our experiments combine stroboscopic techniques that use a high-brightness linear electron accelerator-based x-ray source with pulse-by-pulse timing reconstruction for femtosecond resolution, allowing quantitative characterization of the interatomic potential energy surface of the highly excited solid.     

Atomic-scale visualization of inertial dynamics

The motion of atoms on interatomic potential energy surfaces is fundamental to the dynamics of liquids and solids. An accelerator-based source of femtosecond x-ray pulses allowed us to follow directly atomic displacements on an optically modified energy landscape, leading eventually to the transition from crystalline solid to disordered liquid. We show that, to first order in time, the dynamics are inertial, and we place constraints on the shape and curvature of the transition-state potential energy surface. Our measurements point toward analogies between this nonequilibrium phase transition and the short-time dynamics intrinsic to equilibrium liquids.     

Time-resolved investigation of coherently controlled electric currents at a metal surface

Studies of current dynamics in solids have been hindered by insufficiently brief trigger signals and electronic detection speeds. By combining a coherent control scheme with photoelectron spectroscopy, we generated and detected lateral electron currents at a metal surface on a femtosecond time scale with a contact-free experimental setup. We used coherent optical excitation at the light frequencies omega(a) and omega(a)/2 to induce the current, whose direction was controlled by the relative phase between the phase-locked laser excitation pulses. Time- and angle-resolved photoelectron spectroscopy afforded a direct image of the momentum distribution of the excited electrons as a function of time. For the first (n = 1) image-potential state of Cu(100), we found a decay time of 10 femtoseconds, attributable to electron scattering with steps and surface defects.     

Electron solvation in finite systems: femtosecond dynamics of iodide. (Water)n anion clusters

Electron solvation dynamics in photoexcited anion clusters of I-(D2O)n=4-6 and I-(H2O)4-6 were probed by using femtosecond photoelectron spectroscopy (FPES). An ultrafast pump pulse excited the anion to the cluster analog of the charge-transfer-to-solvent state seen for I- in aqueous solution. Evolution of this state was monitored by time-resolved photoelectron spectroscopy using an ultrafast probe pulse. The excited n = 4 clusters showed simple population decay, but in the n = 5 and 6 clusters the solvent molecules rearranged to stabilize and localize the excess electron, showing characteristics associated with electron solvation dynamics in bulk water. Comparison of the FPES of I-(D2O)n with I-(H2O)n indicates more rapid solvation in the H2O clusters.     

Ultrafast electron localization dynamics following photo-induced charge transfer

Molecular dynamics occurring in the earliest stages following photo-induced charge transfer were investigated. Femtosecond time-resolved absorption anisotropy measurements on [Ru(bpy)(3)](2+), where bpy is 2,2'-bipyridine, reveal a time dependence in nitrile solutions attributed to initial delocalization of the excited state over all three ligands followed by charge localization onto a single ligand. The localization process is proposed to be coupled to nondiffusive solvation dynamics. In contrast, measurements sampling population dynamics show spectral evolution associated with wave packet motion on the excited state surface that is independent of solvent. The results therefore reveal two important contributions to the evolution of charge transfer states in condensed phase, one that is strongly coupled to the surrounding environment and another that follows a potential internal to the molecule.     

Picometer-scale electronic control of molecular dynamics inside a single molecule

Tunneling electrons from a low-temperature (5 kelvin) scanning tunneling microscope were used to control, through resonant electronic excitation, the molecular dynamics of an individual biphenyl molecule adsorbed on a silicon(100) surface. Different reversible molecular movements were selectively activated by tuning the electron energy and by selecting precise locations for the excitation inside the molecule. Both the spatial selectivity and energy dependence of the electronic control are supported by spectroscopic measurements with the scanning tunneling microscope. These experiments demonstrate the feasibility of controlling the molecular dynamics of a single molecule through the localization of the electronic excitation inside the molecule.     

Femtosecond dynamics of electron localization at interfaces

The dynamics of two-dimensional small-polaron formation at ultrathin alkane layers on a silver(111) surface have been studied with femtosecond time- and angle-resolved two-photon photoemission spectroscopy. Optical excitation creates interfacial electrons in quasi-free states for motion parallel to the interface. These initially delocalized electrons self-trap as small polarons in a localized state within a few hundred femtoseconds. The localized electrons then decay back to the metal within picoseconds by tunneling through the adlayer potential barrier. The energy dependence of the self-trapping rate has been measured and modeled with a theory analogous to electron transfer theory. This analysis determines the inter- and intramolecular vibrational modes of the overlayer responsible for self-trapping as well as the relaxation energy of the overlayer molecular lattice. These results for a model interface contribute to the fundamental picture of electron behavior in weakly bonded solids and can lead to better understanding of carrier dynamics in many different systems, including organic light-emitting diodes.     

Electron solvation in two dimensions

Ultrafast two-photon photoemission has been used to study electron solvation at two-dimensional metal/polar-adsorbate interfaces. The molecular motion that causes the excess electron solvation is manifested as a dynamic shift in the electronic energy. Although the initially excited electron is delocalized in the plane of the interface, interactions with the adsorbate can lead to its localization. A method for determining the spatial extent of the localized electron in the plane of the interface has been developed. This spatial extent was measured to be on the order of a single adsorbate molecule.     

Femtosecond multidimensional imaging of a molecular dissociation

The coupled electronic and vibrational motions governing chemical processes are best viewed from the molecule's point of view-the molecular frame. Measurements made in the laboratory frame often conceal information because of the random orientations the molecule can take. We used a combination of time-resolved photoelectron spectroscopy, multidimensional coincidence imaging spectroscopy, and ab initio computation to trace a complete reactant-to-product pathway-the photodissociation of the nitric oxide dimer-from the molecule's point of view, on the femtosecond time scale. This method revealed an elusive photochemical process involving intermediate electronic configurations.     

Atomic-scale coupling of photons to single-molecule junctions

Spatial resolution at the atomic scale has been achieved in the coupling of light to single molecules adsorbed on a surface. Electron transfer to a single molecule induced by green to near-infrared light in the junction of a scanning tunneling microscope (STM) exhibited spatially varying probability that is confined within the molecule. The mechanism involves photo-induced resonant tunneling in which a photoexcited electron in the STM tip is transferred to the molecule. The coupling of photons to the tunneling process provides a pathway to explore molecular dynamics with the combined capabilities of lasers and the STM.     

Ultrafast probing of core hole localization in N2

Although valence electrons are clearly delocalized in molecular bonding frameworks, chemists and physicists have long debated the question of whether the core vacancy created in a homonuclear diatomic molecule by absorption of a single x-ray photon is localized on one atom or delocalized over both. We have been able to clarify this question with an experiment that uses Auger electron angular emission patterns from molecular nitrogen after inner-shell ionization as an ultrafast probe of hole localization. The experiment, along with the accompanying theory, shows that observation of symmetry breaking (localization) or preservation (delocalization) depends on how the quantum entangled Bell state created by Auger decay is detected by the measurement.     

Harnessing attosecond science in the quest for coherent X-rays

Modern laser technology has revolutionized the sensitivity and precision of spectroscopy by providing coherent light in a spectrum spanning the infrared, visible, and ultraviolet wavelength regimes. However, the generation of shorter-wavelength coherent pulses in the x-ray region has proven much more challenging. The recent emergence of high harmonic generation techniques opens the door to this possibility. Here we review the new science that is enabled by an ability to manipulate and control electrons on attosecond time scales, ranging from new tabletop sources of coherent x-rays to an ability to follow complex electron dynamics in molecules and materials. We also explore the implications of these advances for the future of molecular structural characterization schemes that currently rely so heavily on scattering from incoherent x-ray sources.     

Deciphering the reaction dynamics underlying optimal control laser fields

Femtosecond high-resolution pump-probe experiments have been used together with theoretical ab initio quantum calculations and wave packet dynamics simulations to decode an optimal femtosecond pulse that is generated from adaptive learning algorithms. This pulse is designed to maximize the yield of the organometallic ion CpMn(CO)3 while hindering the competing fragmentation. The sequential excitation and ionization of the target ion are accomplished by an optimized field consisting of two dominant subpulses with optimal frequencies and time delays.     

Inverse velocity dependence of vibrationally promoted electron emission from a metal surface

All previous experimental and theoretical studies of molecular interactions at metal surfaces show that electronically nonadiabatic influences increase with molecular velocity. We report the observation of a nonadiabatic electronic effect that follows the opposite trend: The probability of electron emission from a low-work function surface--Au(111) capped by half a monolayer of Cs--increases as the velocity of the incident NO molecule decreases during collisions with highly vibrationally excited NO(X(2)pi((1/2)), V = 18; V is the vibrational quantum number of NO), reaching 0.1 at the lowest velocity studied. We show that these results are consistent with a vibrational autodetachment mechanism, whereby electron emission is possible only beyond a certain critical distance from the surface. This outcome implies that important energy-dissipation pathways involving nonadiabatic electronic excitations and, furthermore, not captured by present theoretical methods may influence reaction rates at surfaces.     

Observing the multiexciton state in singlet fission and ensuing ultrafast multielectron transfer

Multiple exciton generation (MEG) refers to the creation of two or more electron-hole pairs from the absorption of one photon. Although MEG holds great promise, it has proven challenging to implement, and questions remain about the underlying photo-physical dynamics in nanocrystalline as well as molecular media. Using the model system of pentacene/fullerene bilayers and femtosecond nonlinear spectroscopies, we directly observed the multiexciton (ME) state ensuing from singlet fission (a molecular manifestation of MEG) in pentacene. The data suggest that the state exists in coherent superposition with the singlet populated by optical excitation. We also found that multiple electron transfer from the ME state to the fullerene occurs on a subpicosecond time scale, which is one order of magnitude faster than that from the triplet exciton state.     

Deep-ultraviolet quantum interference metrology with ultrashort laser pulses

Precision spectroscopy at ultraviolet and shorter wavelengths has been hindered by the poor access of narrow-band lasers to that spectral region. We demonstrate high-accuracy quantum interference metrology on atomic transitions with the use of an amplified train of phase-controlled pulses from a femtosecond frequency comb laser. The peak power of these pulses allows for efficient harmonic upconversion, paving the way for extension of frequency comb metrology in atoms and ions to the extreme ultraviolet and soft x-ray spectral regions. A proof-of-principle experiment was performed on a deep-ultraviolet (2 x 212.55 nanometers) two-photon transition in krypton; relative to measurement with single nanosecond laser pulses, the accuracy of the absolute transition frequency and isotope shifts was improved by more than an order of magnitude.     

Measuring picosecond isomerization kinetics via broadband microwave spectroscopy

The rotational spectrum of a highly excited molecule is qualitatively different from its pure rotational spectrum and contains information about the intramolecular dynamics. We have developed a broadband Fourier transform microwave spectrometer that uses chirped-pulse excitation to measure a rotational spectrum in the 7.5- to 18.5-gigahertz range in a single shot and thereby reduces acquisition time sufficiently to couple molecular rotational spectroscopy with tunable laser excitation. After vibrationally exciting a single molecular conformation of cyclopropane carboxaldehyde above the barrier to C-C single-bond isomerization, we applied line-shape analysis of the dynamic rotational spectrum to reveal a product yield and picosecond reaction rate that were significantly different from statistical predictions. The technique should be widely applicable to dynamical studies of radical intermediates, molecular complexes, and conformationally flexible molecules with biological interest.