Femtosecond Dynamics Research Articles

Ultrafast evolution of bulk, surface and surface resonance states in photoexcited hbox {Bi}_{2}hbox {Te}_{3}

We use circular dichroism (CD) in time- and angle-resolved photoemission spectroscopy (trARPES) to measure the femtosecond charge dynamics in the topological insulator (TI) hbox {Bi}_{2}hbox {Te}_{3}. We detect clear CD signatures from topological surface states (TSS) and surface resonance (SR) states. In time-resolved measurements, independently from the pump polarization or intensity, the CD shows a dynamics which provides access to the unexplored electronic evolution in unoccupied states of hbox {Bi}_{2}hbox {Te}_{3}. In particular, we are able to disentangle the unpolarized electron dynamics in the bulk states from the spin-textured TSS and SR states on the femtosecond timescale. Our study demonstrates that photoexcitation mainly involves the bulk states and is followed by sub-picosecond transport to the surface. This provides essential details on intra- and interband scattering in the relaxation process of TSS and SR states. Our results reveal the significant role of SRs in the subtle ultrafast interaction between bulk and surface states of TIs.

Femtosecond dynamics of diphenylpropynylidene in ethanol and dichloromethane

Carbon chains with an odd number of C atoms are reactive intermediates with a high biradical character. Here we report a joint experimental and computational investigation of the dynamics of diphenylpropynylidene, C6H5-C3-C6H5, in dichloromethane and ethanol. The biradical is generated by ultraviolet light from 1,3-diphenyldiazopropyne. Electron paramagnetic resonance spectra are recorded to elucidate the spin multiplicity and geometry of the biradical. In both solvents a triplet ground state at 4 K is verified. Transient absorption spectra provide insight into the fate of the biradical. A study in deaerated dichloromethane permits us to follow the photophysics of diphenylpropynylidene and to extract time constants for its vibrational as well as electronic relaxation. In the presence of oxygen, a more complex photochemistry is observed that permits us to derive a model for the reaction of the biradical with O2. In ethanol, the spectra recorded in the presence and absence of O2 are very similar, which can be explained by the similarity of the chromophores of the reaction products.

Femtosecond solvation dynamics study of hydrophobic and hydrophilic probes in various room temperature ionic liquids (RTILs) containing microemulsions

The locations of hydrophobic and hydrophilic probes in room temperature ionic liquids (RTILs) containing microemulsions have been investigated using femtosecond solvation dynamics study, as the time correlated single photon counting (TCSPC) measurement has limitation in terms of detecting the ultrafast component of relaxation time less than 100 ps. Here, choice of two different RTILs unveils the information about the effect of acyclic and cyclic hydrocarbon chain on solvation dynamics. The exclusive information from dynamic light scattering (DLS) measurement, anisotropy study and the fluorescence correlation spectroscopy (FCS) judiciously help to perform detailed analysis of these systems.

Ultrafast photocurrents in MoSe2 probed by terahertz spectroscopy

We use the terahertz (THz) emission spectroscopy to study femtosecond photocurrent dynamics in the prototypical 2D semiconductor, transition metal dichalcogenide MoSe2. We identify several distinct mechanisms producing THz radiation in response to an ultrashort (30 fs) optical excitation in a bilayer (BL) and a multilayer (ML) sample. In the ML, the THz radiation is generated at a picosecond timescale by out-of-plane currents due to the drift of photoexcited charge carriers in the surface electric field. The BL emission is generated by an in-plane shift current. Finally, we observe oscillations at about 23 THz in the emission from the BL sample. We attribute the oscillations to quantum beats between two excitonic states with energetic separation of ∼100 meV.

Protein Mass-Modulated Effects in Alkaline Phosphatase.

Recent experimental studies engaging isotopically substituted protein (heavy protein) have revealed that many, but not all, enzymatic systems exhibit altered chemical steps in response to an altered mass. The results have been interpreted as femtosecond protein dynamics at the active site being linked (or not) to transition-state barrier crossing. An altered enzyme mass can influence several kinetic parameters (kcat, Km, and kchem) in amounts of ≤30% relative to light enzymes. An early report on deuterium-labeled Escherichia coli alkaline phosphatase (AP) showed an unusually large enzyme kinetic isotope effect on kcat. We examined steady-state and chemical step properties of native AP, [2H]AP, and [2H,13C,15N]AP to characterize the role of heavy enzyme protein dynamics in reactions catalyzed by AP. Both [2H]- and [2H,13C,15N]APs showed unaltered steady-state and single-turnover rate constants. These findings characterize AP as one of the enzymes in which mass-dependent catalytic site dynamics is dominated by reactant-linked atomic motions. Two catalytic site zinc ions activate the oxygen nucleophiles in the catalytic site of AP. The mass of the zinc ions is unchanged in light and heavy APs. They are essentially linked to catalysis and provide a possible explanation for the loss of linkage between catalysis and protein mass in these enzymes.

Transient absorption, femtosecond dynamics, vibrational coherence and molecular modelling of the photoisomerization of N-salicylidene-o-aminophenol in solution.

This article presents a study of the excited state relaxation dynamics of N-salicylidene-o-aminophenol (SOAP) in ethanol solution. Femtosecond transient absorption (TA) spectroscopy and theoretical calculations are used in combination to establish the mechanism of the excited state relaxation and type of molecular species involved in the accompanying phototransformations. TA spectra show that upon photoexcitation two SOAP tautomers (E-enol and Z-keto) interconvert by ESIPT. The molecule can subsequently isomerize to the E-keto form of SOAP. An intriguing observation is that the TA spectra of this compound in ethanol show modulations of the signal at the stimulated emission spectral range. It is found that these modulations are due to the coherence of the excited ensemble of molecules whose evolution over time represents a moving wave packet. After Fourier transform of the modulations, two characteristic frequencies are identified. These frequencies refer to the corresponding vibrational modes of the excited state and their nature is elucidated by DFT quantum chemical calculations. The obtained experimental and theoretical data reveal the nature of the vibronic coupling between the ground and excited state and the type of molecular vibrations involved in the molecular dynamics along the potential surface of the first excited state at the initial moment right after excitation. These vibrations characterize the starting point in the excited state dynamics of the molecule toward Z-E isomerization of the keto form of SOAP. This study provides a comprehensive picture of the dynamic processes taking place upon photoexcitation of the compound, which might enable control over the various relaxation channels.

Temperature-Dependent Ultrafast Response and π-Plasmon Dynamics in Single-Walled Carbon Nanotubes.

Temperature-dependent femtosecond time-resolved carrier relaxation dynamics has been studied in thin films of single-walled carbon nanotubes. An early time evolution of the photoexcited relaxation shows evidence of superimposed transient bleaching and induced photo absorption of almost similar strengths, whereas at longer times it is governed by slow recovery of long-lived dark excitons. After about 3 ps, the signal is dictated by the slowest negative relaxation component attributed to the low-energy π-plasmons. An absorption trough near 500 fs in the ultrafast response evolves with the increasing sample temperature. This particular feature is masked by the reduced induced transmission at room temperature and above. We have estimated the electron-phonon coupling constant to be ∼0.86 from the linear temperature dependence of the slow relaxation time constant. More such studies can help advance the understanding of the intrinsic charge and energy loss mechanisms to improve the efficiency of the optoelectronic devices based on them.

Imaging multiphoton ionization dynamics of CH3I at a high repetition rate XUV free-electron laser

XUV multiphoton ionization of molecules is commonly used in free-electron laser experiments to study charge transfer dynamics. However, molecular dissociation and electron dynamics, such as multiple photon absorption, Auger decay, and charge transfer, often happen on competing time scales, and the contributions of individual processes can be difficult to unravel. We experimentally investigate the Coulomb explosion dynamics of methyl iodide upon core–hole ionization of the shallow inner-shell of iodine (4d) and classically simulate the fragmentation by phenomenologically introducing ionization dynamics and charge transfer. Under our experimental conditions with medium fluence and relatively long XUV pulses (∼75 fs), we find that fast Auger decay prior to charge transfer significantly contributes to the charging mechanism, leading to a yield enhancement of higher carbon charge states upon molecular dissociation. Furthermore, we argue for the existence of another charging mechanism for the weak fragmentation channels leading to triply charged carbon atoms. This study shows that classical simulations can be a useful tool to guide the quantum mechanical description of the femtosecond dynamics upon multiphoton absorption in molecular systems.

Coherent Vibration and Femtosecond Dynamics of the Platinum Complex Oligomers upon Intermolecular Bond Formation in the Excited State

AbstractFemtosecond time‐resolved absorption and picosecond time‐resolved emission measurements were carried out for highly concentrated aqueous solutions of K2[Pt(CN)4] to investigate excited‐state dynamics of the [Pt(CN)42−] oligomers formed with metallophilic interactions. Time‐resolved absorption spectra exhibit complicated dynamics that are represented with five time constants. Among them, the 90‐ps and 400‐ps dynamics were assigned to the S1 → T1 intersystem crossing of the trimer and tetramer coexisting in the solution by comparison with the fluorescence decays. Clear oscillations of transient absorption were observed in the first few picoseconds, and the frequency‐detected‐wavelength 2D analysis revealed that the 135‐cm−1 and 65‐cm−1 oscillations arise from the Pt–Pt stretch motions of the S1 trimer and S1 tetramer, respectively. The obtained time‐resolved spectroscopic data provide a clear view of the excited‐state dynamics of the [Pt(CN)42−] oligomers in the femto‐/picosecond time region.

Coherent Vibration and Femtosecond Dynamics of the Platinum Complex Oligomers upon Intermolecular Bond Formation in the Excited State.

Femtosecond time-resolved absorption and picosecond time-resolved emission measurements were carried out for highly concentrated aqueous solutions of K2 [Pt(CN)4 ] to investigate excited-state dynamics of the [Pt(CN)4 2- ] oligomers formed with metallophilic interactions. Time-resolved absorption spectra exhibit complicated dynamics that are represented with five time constants. Among them, the 90-ps and 400-ps dynamics were assigned to the S1 → T1 intersystem crossing of the trimer and tetramer coexisting in the solution by comparison with the fluorescence decays. Clear oscillations of transient absorption were observed in the first few picoseconds, and the frequency-detected-wavelength 2D analysis revealed that the 135-cm-1 and 65-cm-1 oscillations arise from the Pt-Pt stretch motions of the S1 trimer and S1 tetramer, respectively. The obtained time-resolved spectroscopic data provide a clear view of the excited-state dynamics of the [Pt(CN)4 2- ] oligomers in the femto-/picosecond time region.

Relaxation Dynamics of Excited States in Mn2+-Doped ZnCdS (Core)/ZnS (Shell) Quantum Dots Ions in Propylene Carbonate

It has been shown that luminescence in Mn@Zn0.49Cd0.51S/ZnS quantum dots (QDs) in propylene carbonate is due to a single Mn2+(4T1 → 6A1) band and has a quantum yield of ~24%. The Mn2+(4T1) level is excited through the light absorption in the exciton absorption bands of Zn0.49Cd0.51S/ZnS. The femtosecond dynamics of the difference spectra of Mn@Zn0.49Cd0.51S/ZnS QDs show fast relaxation of the exciton on the subpicosecond–picosecond timescale. At delay times in picosecond range, the band of stimulated luminescence has been detected in difference absorption spectra in the Mn2+(4T1 → 6A1) transition region. A qualitative hypothetical mechanism of nonradiative energy transfer from the exciton to Mn2+(4T1) involving the Auger transition in the trap states has been proposed. The assumption solves the problems of the energy excess of 0.98 eV in the energy transfer to the 3d5 level of Mn and of the conservation of the total spin of the system.

Laser pulse driven control of charge and spin order in the two-dimensional Kondo lattice

Fast and dynamical control of quantum phases is highly desired in the application of quantum phenomena in devices. On the experimental side, ultrafast laser pulses provide an ideal platform to induce femtosecond dynamics in a variety of materials. Here, we show that a laser pulse driven heavy fermion system, can be tuned to dynamically evolve into a phase, which is not present in equilibrium. Using the state-of-the-art time-dependent variational Monte Carlo method, we perform numerical simulations of realistic laser pulses applied to the Kondo Lattice model. By tracking spin and charge degrees of freedom we identify a dynamical phase transition from a charge ordered into a metallic state, while preserving the spin order of the system. We propose to use higher harmonic generation to identify the dynamical phase transition in an ultrafast experiment.

Surface electronic structure and dynamics of lead halide perovskites

A number of studies investigating the electronic structure of well-defined lead halide perovskite surfaces have emerged in the last five years. Surfaces and their interfaces can not only have considerable effects on the performance of devices such as solar cells but also open a window into the intrinsic electronic properties of lead halide perovskites. This is particularly true for angle-resolved photoelectron spectroscopy, which is possibly the technique giving the most direct access to the electronic (band) structure of a material. The pump–probe version of the technique, two-photon photoelectron spectroscopy, gives information about the femtosecond and picosecond electron dynamics following optical excitation. This review summarizes the recent progress made using these surface-sensitive techniques. In addition, differences between the optical and electronic properties between the near-surface (hundreds of nm) and the deep bulk material of single crystals are discussed. We point out critical issues concerning the comparability between individual results arising from the different depths and timescales probed, or from differing environmental conditions such as the temperature or the surrounding atmosphere.

Femtosecond excited state dynamics of stilbene-viologen complexes with a weakly pronounced charge transfer.

The femtosecond dynamics of photoinduced electron transfers in supramolecular donor-acceptor complexes between (E)-bis(18-crown-6)stilbene (D) and tetraperchlorates of 2,7-di(2-ammonioethyl)(2,7-diazapyrenium) (A1), 3,3'-(E)-ethene-1,2-diylbis[1-(3-ammoniopropyl)pyridinium] (A2) and 4,4'-ethane-1,2-diylbis[1-(3-ammoniopropyl)pyridinium] (A3) was studied. The acceptors A2 and A3 are weak electron acceptors whose first reduction potentials are equal to -1.0 and -1.2 V (Ag), respectively, while A1 is a strong acceptor with a reduction potential of -0.42 V. It was shown that the back electron transfer time in CT-states of the complexes D·A2 and D·A3 is 30-40 ps, which is approximately 50 times greater than the analogous time for the charge transfer complexes studied earlier. The complex D·A1 is characterized by ultrafast back electron transfer (770 fs). The relaxation pathway of excited states of D·A1 depends on the wavelength of the excitation light. When excited at 356 nm, the accumulation of a transient locally excited (LE) state with a 250 fs lifetime was observed. But when excited at 425 nm, the formation of the LE-state was not observed.

Hot-Carrier Generation in Plasmonic Nanoparticles: The Importance of Atomic Structure.

Metal nanoparticles are attractive for plasmon-enhanced generation of hot carriers, which may be harnessed in photochemical reactions. In this work, we analyze the coherent femtosecond dynamics of photon absorption, plasmon formation, and subsequent hot-carrier generation through plasmon dephasing using first-principles simulations. We predict the energetic and spatial hot-carrier distributions in small metal nanoparticles and show that the distribution of hot electrons is very sensitive to the local structure. Our results show that surface sites exhibit enhanced hot-electron generation in comparison to the bulk of the nanoparticle. Although the details of the distribution depend on particle size and shape, as a general trend, lower-coordinated surface sites such as corners, edges, and {100} facets exhibit a higher proportion of hot electrons than higher-coordinated surface sites such as {111} facets or the core sites. The present results thereby demonstrate how hot carriers could be tailored by careful design of atomic-scale structures in nanoscale systems.

Femtosecond Transient Absorption Spectra and Dynamics of Carrier Relaxation of Tin Perovskites in the Absence and Presence of Additives.

The effects of additives SnF2 (10%) and EDAI2 (1%) on the dynamics of carrier relaxation of formamidinium tin triiodide (FASnI3) perovskite were studied using femtosecond transient absorption spectra (TAS) with excitation at 600 and 870 nm. The TAS were analyzed according to a parallel sequential kinetic model with a global fit through singular-value decomposition. For excitation at 600 nm, two relaxation paths were found: one involved hot and cold carriers in the bulk state undergoing shallow bulk-defect-mediated charge recombination; the other involved trap carriers in the surface state undergoing deep surface-defect-mediated charge recombination. For excitation at 870 nm, only cold carriers were subjected to the bulk-state relaxation channel. Our spectral results indicate significant effects of the additives on retarding charge recombination in both bulk and surface states as well as decreasing the bandgap renormalization energy, the bandwidth of the photobleaching (PB) band, and the Stokes shift between the PB and photoluminescence bands, explaining how the device performance of FASnI3 solar cells became enhanced in the presence of SnF2 and EDAI2.

The shape of the electric dipole function determines the sub-picosecond dynamics of anharmonic vibrational polaritons

Vibrational strong coupling has emerged as a promising route for manipulating the reactivity of molecules inside infrared cavities. We develop a full-quantum methodology to study the unitary dynamics of a single anharmonic vibrational mode interacting with a quantized infrared cavity field. By comparing multi-configurational time-dependent Hartree simulations for an intracavity Morse oscillator with an equivalent formulation of the problem in Hilbert space, we describe for the first time the essential role of permanent dipole moments in the femtosecond dynamics of vibrational polariton wavepackets. We classify molecules into three general families according to the shape of their electric dipole function de(q) along the vibrational mode coordinate q. For polar species with a positive slope of the dipole function at equilibrium, an initial diabatic light-matter product state without vibrational or cavity excitations evolves into a polariton wavepacket with a large number of intracavity photons for interaction strengths at the conventional onset of ultrastrong coupling. This buildup of the cavity photon amplitude is accompanied by an effective lengthening of the vibrational mode that is comparable with a laser-induced vibrational excitation in free space. In contrast, polar molecules with a negative slope of the dipole function experience an effective mode shortening, under equivalent coupling conditions. We validate our predictions using realistic ab initio ground state potentials and dipole functions for HF and CO2 molecules. We also propose a non-adiabatic state preparation scheme to generate vibrational polaritons with molecules near infrared nanoantennas for the spontaneous radiation of infrared quantum light.

Ultrafast Nonlinear Spectroscopy in (111) Oriented Bismuth Ferrite Oxide

We fabricated a (111) oriented epitaxial thin film of ferroelectric iron oxide, BiFeO3 and investigated the nonlinear optical properties and its femtosecond dynamics. The angle dependence of second...

Time-resolved VUV ARPES at 10.8 eV photon energy and MHz repetition rate

The quest for mapping the femtosecond dynamics of the electronic band structure of complex materials over their full first Brillouin zone is pushing the development of schemes to efficiently generate ultrashort photon pulses in the VUV energy range. At present, the critical aspect in time- and angle-resolved photoelectron spectroscopy (TR-ARPES) is to combine a high photon energy with high photoemission count rates and a narrow pulse-bandwidth, necessary to achieve high energy resolution, while preserving a good time resolution and mitigating space-charge effects. Here we describe a novel approach to produce light pulses at 10.8 eV, combining high repetition rate operation (1–4 MHz), high energy resolution (∼26 meV) and space-charge free operation, with a time-resolution of ∼700 fs. These results have been achieved by generating the ninth harmonic of a Yb fiber laser, through a phase-matched process of third harmonic generation in Xenon of the laser third harmonic. The full up-conversion process is driven by a seed pulse energy as low as 10 μJ, hence is easily scalable to multi-MHz operation. This source opens the way to TR-ARPES experiments for the investigation of the electron dynamics over the full first Brillouin zone of most complex materials, with unprecedented energy and momentum resolutions and high count rates. The performances of the setup are tested by TR-ARPES on the topological insulator Bi2Se3.

Method for developing a sub-10 fs ultrafast electron diffraction technology.

The experimental observation of femtosecond dynamics in atoms and molecules by stroboscopic technologies utilizing x ray or electron flashes has attracted much attention and has rapidly developed. We propose a feasible ultrafast electron diffraction (UED) technology with high brightness and a sub-10 fs temporal resolution. We previously demonstrated a UED system with an overall temporal resolution of 31 fs by using an RF photoelectron gun and a 90° achromatic bending structure. This UED structure enabled a bunch duration of 25 fs and a low timing jitter of less than 10 fs while maintaining a high bunch charge of 0.6 pC. In this paper, we demonstrate a simple way to further compress the electron bunch duration to sub-10 fs based on installing an energy filter in the dispersion section of the achromatic bend. The energy filter removes the electrons belonging to nonlinear parts of the phase space. Through numerical simulations, we demonstrate that the electron bunches can be compressed, at the sample position, to a 6.2 fs (rms) duration for a 100 fC charge. This result suggests that the energy filtering approach is more viable and effective than complicated beam-shaping techniques that commonly handle the nonlinear distribution of the electron beam. Furthermore, a gas-filled hollow core fiber compressor and a Ti:sapphire amplifier are used to implement pump laser pulses of less than 5 fs (rms). Thus, we could present the full simulation results of a sub-10 fs UED, and we believe that it will be one of the technical prototypes to challenge the sub-fs time resolution.