Femtosecond Pump-probe Spectroscopy Research Articles

Coherent phonons in incommensurate LaVS3 crystal

In this Letter, we investigate coherent phonon dynamics in the incommensurate LaVS3 crystal by femtosecond pump-probe spectroscopy. Two coherent phonon modes are systematically observed in the transient reflectivity, centered at 1.8 and 2.85 THz, respectively, while a third mode centered at 4.5 THz is observed only at high pump fluence. The experimental results obtained at two different polarization configurations as well as a comparison with recent theoretical results allow to assign the two main modes to the interlayer shearing mode and to an intralayer mode, respectively. Two possible assignments are discussed for the third mode, by invoking a possible emergence of nonlinear phonon processes.

Specificity of Photochemical Energy Conversion in PhotosystemI from the Green Microalga Chlorella ohadii.

Primary excitation energy transfer and charge separation in photosystemI(PSI) from the extremophile desert green alga Chlorella ohadii grown in low light were studied using broadband femtosecond pump-probe spectroscopy in the spectral range from 400 to 850nm and in the time range from 50fs to 500ps. Photochemical reactions were induced by the excitation into the blue and red edges of the chlorophyll Qy absorption band and compared with similar processes in PSI from the cyanobacterium Synechocystissp. PCC6803. When PSI from C.ohadii was excited at 660nm, the processes of energy redistribution in the light-harvesting antenna complex were observed within a time interval of up to 25ps, while formation of the stable radical ion pair P700+A1- was kinetically heterogeneous with characteristic times of 25 and 120ps. When PSI was excited into the red edge of the Qy band at 715nm, primary charge separation reactions occurred within the time range of 7ps in half of the complexes. In the remaining complexes, formation of the radical ion pair P700+A1- was limited by the energy transfer and occurred with a characteristic time of 70ps. Similar photochemical reactions in PSI from Synechocystis6803 were significantly faster: upon excitation at 680nm, formation of the primary radical ion pairs occurred with a time of 3ps in ~30% complexes. Excitation at 720nm resulted in kinetically unresolvable ultrafast primary charge separation in 50% complexes, and subsequent formation of P700+A1- was observed within 25ps. The photodynamics of PSI from C.ohadii was noticeably similar to the excitation energy transfer and charge separation in PSI from the microalga Chlamydomonas reinhardtii; however, the dynamics of energy transfer in C.ohadii PSI also included slower components.

Femtosecond optical studies of the primary charge separation reactions in far-red photosystem II from Synechococcus sp. PCC 7335

Primary processes of light energy conversion by Photosystem II (PSII) were studied using femtosecond broadband pump-probe absorption difference spectroscopy. Transient absorption changes of core complexes isolated from the cyanobacterium Synechococcus sp. PCC 7335 grown under far-red light (FRL-PSII) were compared with the canonical Chl a containing spinach PSII core complexes upon excitation into the red edge of the Qy band. Absorption changes of FRL-PSII were monitored at 278 K in the 400–800 nm spectral range on a timescale of 0.1–500 ps upon selective excitation at 740 nm of four chlorophyll (Chl) f molecules in the light harvesting antenna, or of one Chl d molecule at the ChlD1 position in the reaction center (RC) upon pumping at 710 nm. Numerical analysis of absorption changes and assessment of the energy levels of the presumed ion-radical states made it possible to identify PD1+ChlD1− as the predominant primary charge-separated radical pair, the formation of which upon selective excitation of Chl d has an apparent time of ∼1.6 ps. Electron transfer to the secondary acceptor pheophytin PheoD1 has an apparent time of ∼7 ps with a variety of excitation wavelengths. The energy redistribution between Chl a and Chl f in the antenna occurs within 1 ps, whereas the energy migration from Chl f to the RC occurs mostly with lifetimes of 60 and 400 ps. Potentiometric analysis suggests that in canonical PSII, PD1+ChlD1− can be partially formed from the excited (PD1ChlD1)* state.

Photophysics of Benzoxazole and Dicyano Functionalised Diketopyrrolopyrrole Derivatives: Insights into Ultrafast Processes and the Triplet State.

Diketopyrrolopyrrole (DPP) functionalised with an electron donating unit acts as a donor-acceptor molecules that have shown potential for application in dyes and photovoltaics. These molecules offer broad absorption/emission properties and structure-dependent dynamics. In this study, we used femtosecond pump-probe spectroscopy to investigate the photo-initiated dynamics of thiophene linked DPP derivatives. The thio-DPPs are further functionalised by different electrons withdrawing terminal groups, namely benzoxazole and thiophene dicyanide. The benzoxazole derivative is strongly emissive and directly relaxes directly to the ground state chloroform solution. Thiophene dicyanide derivative exhibits distinct spectral evolution in the first 10 ps, associated with structural and vibronic process. Later, it crosses over to the triplet state with a yield of 20 %. In the solid-state (thin film), we observed a signal that resembles singlet fission. However, upon careful analysis of temperature-dependent steady state absorbance spectra, we conclude that these features are due to laser-induced thermal artifacts. We describe a simplified excited state evolution in the thin film that does not include any additional excited states. These findings have significant implications for the analysis of triplet formation, which plays a major role in the photophysics of many organic materials.

Ultrafast Vibrational Wave Packet Dynamics of the Aqueous Guanine Radical Anion Induced by Photodetachment.

Studying the ultrafast dynamics of ionized aqueous biomolecules is important for gaining an understanding of the interaction of ionizing radiation with biological matter. Guanine plays an essential role in biological systems as one of the four nucleobases that form the building blocks of deoxyribonucleic acid (DNA). Guanine radicals can induce oxidative damage to DNA, particularly due to the lower ionization potential of guanine compared to the other nucleobases, sugars, and phosphate groups that are constituents of DNA. This study utilizes femtosecond optical pump-probe spectroscopy to observe the ultrafast vibrational wave packet dynamics of the guanine radical anion launched by photodetachment of the aqueous guanine dianion. The vibrational wave packet motion is resolved into 11 vibrational modes along which structural reorganization occurs upon photodetachment. These vibrational modes are assigned with the aid of density functional theory (DFT) calculations. Our work sheds light on the ultrafast vibrational dynamics following the ionization of nucleobases in an aqueous medium.

Vibrational wave-packet dynamics of the silver pentamer probed by femtosecond NeNePo spectroscopy.

Vibrational wave-packet dynamics on the ground electronic state of the neutral silver pentamer (Ag5) are studied by femtosecond (fs) pump-probe spectroscopy using the 'negative ion - to neutral - to positive ion' (NeNePo) excitation scheme. A vibrational wave packet is prepared on the 2A1 state of Ag5via photodetachment of mass-selected, cryogenically cooled Ag5- anions using a fs pump pulse. The temporal evolution of the vibrational wave packet is then probed by an ultrafast probe pulse via resonant multiphoton ionization to Ag5+. Frequency analysis of the fs NeNePo transients for pump-probe delay times from 0.2 to 8 ps reveals three primary beating frequencies at 157 cm-1, 101 cm-1 and 56 cm-1 as well as four weaker features. A comparison of these experimentally obtained beating frequencies to harmonic normal mode frequencies calculated from electronic structure calculations confirms that Ag5 in the gas phase adopts a planar trapezoidal geometry, similar to that previously observed in solid argon. The dependence of the ionization yield on the laser polarization indicates a s-d wave electron photodetachment from a 'p-type' occupied molecular orbital of Ag5. Franck-Condon analysis shows that both processes, photodetachment and subsequent photoionization determine the beating frequencies probed in the time-dependent cation yield. The present study extends the applicability of fs NeNePo spectroscopy to characterize the vibrational spectra in the far-IR frequency range in the absence of perturbations from a medium or a messenger atom to mass-selected neutral metal clusters with more than three atoms in the ground electronic states.

Multiple coherent amplitude modes and exciton-phonon coupling in quasi-one-dimensional excitonic insulator Ta2NiSe5.

An excitonic insulator (EI) is an intriguing correlated electronic phase of condensed excitons. Ta2NiSe5 is a model material for investigating condensed excitonic states. Herein, femtosecond pump-probe spectroscopy is used to study the coherent phonon dynamics and associated exciton-phonon coupling in single-crystal Ta2NiSe5. The reflectivity time series consists of exponential decay due to hot carriers and damped oscillations due to the Ag phonon vibration. Given the in-plane anisotropic thermal conductivity of Ta2NiSe5, coherent phonon oscillations are stronger with perpendicular polarization to its quasi-one-dimensional chains. The 1-, 2-, and 4-THz vibration modes show coherent amplitude responses in the EI phase of Ta2NiSe5 with increasing temperature, totally different from those of normal coherent phonons (the 3- and 3.7-THz modes). The amplitude modes at higher frequencies decouple with the EI order parameter at lower temperatures, as supported by theoretical analysis with a model Hamiltonian of the exciton-phonon coupling system. Our work provides valuable insights into the character of the EI order parameter and its coupling to multiple coherent amplitude modes.

Reinvestigation on primary processes of PSII-dimer from Thermosynechococcus vulcanus by femtosecond pump-probe spectroscopy.

Cyanobacterial photosynthetic apparatus efficiently capture sunlight, and the energy is subsequently transferred to photosystem I (PSI) and II (PSII), to produce electrochemical potentials. PSII is a unique membrane protein complex that photo-catalyzes oxidation of water and majorly contains photosynthetic pigments of chlorophyll a and carotenoids. In the present study, the ultrafast energy transfer and charge separation dynamics of PSII from a thermophilic cyanobacterium Thermosynechococcus vulcanus were reinvestigated by femtosecond pump-probe spectroscopic measurements under low temperature and weak intensity excitation condition. The results imply the two possible models of the energy transfers and subsequent charge separation in PSII. One is the previously suggested "transfer-to-trapped limit" model. Another model suggests that the energy transfers from core CP43 and CP47 antennas to the primary electron donor ChlD1 with time-constants of 0.71ps and 3.28ps at 140K (0.17 and 1.33ps at 296K), respectively and that the pheophytin anion (PheoD1-) is generated with the time-constant of 43.0ps at 140K (14.8ps at 296K) upon excitation into the Qy band of chlorophyll a at 670nm. The secondary electron transfer to quinone QA: PheoD1-QA → PheoD1QA- is observed with the time-constant of 650ps only at 296K. On the other hand, an inefficient β-carotene → chlorophyll a energy transfer (33%) occurred after excitation to the S2 state of β-carotene at 500nm. Instead, the carotenoid triplet state appeared in an ultrafast timescale after excitation at 500nm.

Ultrafast Plasmonic Hot Hole Transfer and Plasmon Dynamics in a Dual Plasmonic Au@p‐Cu2−xSe Heterostructure

AbstractMetal‐semiconductor heterostructures have significant potential in harvesting plasmon induced hot charge carriers for photocatalytic and photovoltaic devices. Despite numerous studies, the field of hot hole transfer in heterostructures remains unexplored. In this work, the plasmon dynamics of a dual plasmonic core–shell Au@p‐Cu2−xSe heterostructure are investigated with the aid of femtosecond broadband pump probe spectroscopy. Ultrafast studies reveal that hot holes generated within the d and sp band after 400 and 800 nm excitations are injected from Au to copper selenide. Hot hole transfer substantially reduces the transient signal intensity and electron phonon relaxation time for Au plasmon. Increment in the transient signal intensity and slower kinetics for the semiconducting plasmon of Au@Cu2−xSe validate the hot hole transfer in the valence band of copper selenide. Fluence dependent studies reveal that d band hot holes extraction is more efficient than that of sp band hot holes.

Revealing core-valence interactions in solution with femtosecond X-ray pump X-ray probe spectroscopy

Femtosecond pump-probe spectroscopy using ultrafast optical and infrared pulses has become an essential tool to discover and understand complex electronic and structural dynamics in solvated molecular, biological, and material systems. Here we report the experimental realization of an ultrafast two-color X-ray pump X-ray probe transient absorption experiment performed in solution. A 10 fs X-ray pump pulse creates a localized excitation by removing a 1s electron from an Fe atom in solvated ferro- and ferricyanide complexes. Following the ensuing Auger–Meitner cascade, the second X-ray pulse probes the Fe 1s → 3p transitions in resultant novel core-excited electronic states. Careful comparison of the experimental spectra with theory, extracts +2 eV shifts in transition energies per valence hole, providing insight into correlated interactions of valence 3d with 3p and deeper-lying electrons. Such information is essential for accurate modeling and predictive synthesis of transition metal complexes relevant for applications ranging from catalysis to information storage technology. This study demonstrates the experimental realization of the scientific opportunities possible with the continued development of multicolor multi-pulse X-ray spectroscopy to study electronic correlations in complex condensed phase systems.

Aggregation-Induced Stimulated Emission of 100% Dye Microspheres.

Dyes with aggregation-induced emission (AIE) properties have gained interests due to their bright luminescence in solid-state aggregates. While fluorescence from AIE dyes have been widely exploited, relatively little is known about aggregation-induced stimulated emission. Here, we investigated stimulated emission of tetraphenylethene (TPE)-based organoboron AIE dyes, TPEQBN, in thin films and in microcavity lasers. Using femtosecond pump-probe spectroscopy, gain coefficients up to 230 cm-1 at 500 nm were measured. Using rate equations, we analyzed concentration- and pump-dependent gain dynamics as well as laser build up dynamics. During laser oscillation, radiative stimulated emission allows high instantaneous quantum yield greater than 90% to be achieved. We fabricated solid-state microspheres made of 100% AIE dyes via microfluidic emulsion and solvent evaporation method. Coupled with high gain and high refractive index of 1.76, microspheres as small as 2 μm in diameter showed lasing by nanosecond pumping with a threshold of ~10 pJ μm-2. Polymer coated, but not bare, microspheres were internalized by live cells and generated narrowband cavity mode emission from within the cytoplasm. Our work shows the potential of AIE dyes as laser materials.

Nuclear quantum dynamics on the ground electronic state of neutral silver dimer 107Ag109Ag probed by femtosecond NeNePo spectroscopy.

The nuclear quantum dynamics on the ground electronic state of the neutral silver dimer 107Ag109Ag are studied by femtosecond (fs) pump-probe spectroscopy using the 'negative ion - to neutral - to positive ion' (NeNePo) excitation scheme. A vibrational wave packet is prepared on the X1Σ+g state of Ag2via photodetachment of mass-selected, cryogenically cooled Ag2- using a first ultrafast pump laser pulse. The temporal evolution of the wave packet is then probed by an ultrafast probe pulse via resonant multiphoton ionization to Ag2+. Frequency analysis of the fs-NeNePo spectra obtained for a single isotopologue and pump-probe delay times up to 60 ps yields the harmonic (ωe = 192.2 cm-1), quadratic anharmonic (ωexe = 0.637 cm-1) and cubic anharmonic (ωeye = 3 × 10-4 cm-1) constants for the X1Σ+g state of neutral Ag2. The fs-NeNePo spectra obtained at different pump wavelengths provide insight into the excitation mechanism. At a pump wavelength of 510 nm instead of 1010 nm, resonant excitation of a short-lived electronically excited state of the anion followed by autodetachment results in population of higher-energy vibrational levels of the neutral ground state. In contrast, at 1140 nm dynamics with a slightly shorter beating period and different relative phase are observed. The present study demonstrates that isotopologue-specific fs-NeNePo spectroscopy provides accurate vibrational constants of mass-selected neutral clusters in their electronic ground state in the terahertz spectral region, which remains difficult to obtain directly in the frequency domain with any other type of spectroscopy of comparable sensitivity.

Enhanced Optical Response in Au Nanopillar/La0.67Sr0.33MnO3 Film Composites: Implications for Magnetooptical Devices

Metal oxide vertically aligned nanocomposite thin films have been of considerable interest for hot-carrier-based light harvesting and active plasmonic applications. Herein, we present femtosecond pump–probe spectroscopy studies on a nanocomposite thin film with plasmonic Au nanopillars vertically aligned in a ferromagnetic La0.67Sr0.33MnO3 (LSMO) matrix. Our measurements reveal that the carrier decay of Au/LSMO films qualitatively follows that of pure LSMO with a two-component relaxation. In the presence of Au nanopillars, the charge generation within the LSMO film is enhanced by a factor of ∼40, and the spin–lattice relaxation time associated with demagnetization is substantially decreased from 259.6 to 7.7 ps. The enhanced nonequilibrium dynamics and energy transfer between the lattice and spin system in the Au/LSMO films can be well modeled using an extended three-temperature model. These Au/LSMO thin films can be potentially useful in ultrafast photoelectric and magnetooptical applications.

Transient THz Emission and Effective Mass Determination in Highly Resistive GaAs Crystals Excited by Femtosecond Optical Pulses

We present comprehensive studies on the emission of broadband, free-space THz transients from several highly resistive GaAs samples excited by femtosecond optical pulses. Our test samples are characterized by different degrees of disorder, ranging from nitrogen-implanted to semi-insulating and annealed semi-insulating GaAs crystals. In our samples, we clearly observed transient THz emissions due to the optical rectification effect, as well as due to the presence of the surface depletion electrical field. Next, we arranged our experimental setup in such way that we could observe directly how the amplitude of surface-emitted THz optical pulses is affected by an applied, in-plane magnetic field. We ascribe this effect to the Lorentz force that additionally accelerates optically excited carriers. The magnetic-field factor η is a linear function of the applied magnetic field and is the largest for an annealed GaAs sample, while it is the lowest for an N-implanted GaAs annealed at the lowest (300 °C) temperature. The latter is directly related to the longest and shortest trapping times, respectively, measured using a femtosecond optical pump-probe spectroscopy technique. The linear dependence of the factor η on the trapping time enabled us to establish that, for all samples, regardless of their crystalline structure, the electron effective mass was equal to 0.059 of the electron mass m0, i.e., it was only about 6% smaller than the generally accepted 0.063m0 value for GaAs with a perfect crystalline structure.

Optical cavity-mediated exciton dynamics in photosynthetic light harvesting 2 complexes

Strong light-matter interaction leads to the formation of hybrid polariton states and alters the photophysical dynamics of organic materials and biological systems without modifying their chemical structure. Here, we experimentally investigated a well-known photosynthetic protein, light harvesting 2 complexes (LH2) from purple bacteria under strong coupling with the light mode of a Fabry-Perot optical microcavity. Using femtosecond pump probe spectroscopy, we analyzed the polariton dynamics of the strongly coupled system and observed a significant prolongation of the excited state lifetime compared with the bare exciton, which can be explained in terms of the exciton reservoir model. Our findings indicate the potential of tuning the dynamic of the whole photosynthetic unit, which contains several light harvesting complexes and reaction centers, with the help of strong exciton-photon coupling, and opening the discussion about possible design strategies of artificial photosynthetic devices.

(Cd,Mg)Te crystals for picosecond-response optical-to-x-ray radiation detectors.

We demonstrate a photodetector sensitive to both optical and x-ray picosecond pulses based on our in-house grown cadmium magnesium telluride (Cd,Mg)Te single crystal. Specifically, we developed In-doped Cd0.96Mg0.04Te material and discuss its femtosecond optical photoresponse, as well as the detector performance, such as <100-pA dark current and up to 0.22-mA/W responsivity for 780-nm wavelength optical radiation. The detector exposed to Ti fluorescence (K alpha) x-ray pulses at 4.5keV, generated by a free-electron laser beam with the central energy of 9.8keV and <100fs pulse width, exhibited readout-electronics-limited 200-ps full-width-at-half-maximum photoresponse, demonstrating that it is suitable for coarse timing in free-electron laser x-ray/optical femtosecond pump-probe spectroscopy applications.

Light-Stimulated Luminescence Control of Lead Halide-Based Perovskite Nanocrystals Coupled with Photochromic Molecules via Electron and Energy Transfer.

Photoswitchable nanomaterials are key materials in the development of advanced imaging techniques, such as super-resolution fluorescence microscopy. The combination of perovskite CsPbBr3 nanocrystals (NCs) with bright photoluminescence (PL) emission and diarylethenes (DAEs) with structural changes in response to ultraviolet (UV) and visible light is a promising candidate system. Herein, CsPbBr3 NCs are coupled with photochromic DAE molecules to control the PL emission from the NCs by light stimulation. The PL emission is successfully switched ON and OFF by alternating UV and visible light irradiation. Time-resolved PL emission studies suggest that Förster resonance energy transfer from CsPbBr3 NCs to the closed-ring form of DAE occurs after UV irradiation, and the PL emission is quenched. Upon visible-light irradiation, DAE is converted to the open-ring isomer, and the PL emission is restored. Femtosecond pump-probe spectroscopy reveals that light stimulation induces not only energy transfer but also photoinduced electron transfer in the NC-DAE pair on the picosecond timescale to form DAE radicals. Thus, it is suggested that the holes residing in the NCs react with the NCs, degrading the PL emission. Stable PL switching is realized using 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) as a hole scavenger to avoid the reaction between the holes and NCs.

Ultrafast Excitonic Response in Two-Dimensional Hybrid Perovskites Driven by Intense Midinfrared Pulses.

Two-dimensional organic-inorganic hybrid perovskites (2DHPs) are natural quantum-well-like materials, in which strong quantum and dielectric confinement effects due to the organic spacers give rise to tightly bound excitons with large binding energy. To examine the mutual interactions between the organic spacer cations and the inorganic charge-residing octahedral framework in 2DHPs, here we perform femtosecond pump-probe spectroscopy by direct vibrational pumping of the organic spacers, followed by a visible-to-ultraviolet probe covering their excitonic resonances. Measurements on prototypical lead-bromide based 2DHP compounds, (BA)_{2}PbBr_{4} and (BA)_{2}(FA)Pb_{2}Br_{7} (BA^{+}=butylammonium; FA^{+}=formamidinium), reveal two distinct regimes of the temporal response. The first regime is dominated by a pump-induced transient expansion of the organic spacer layers that reduces the exciton oscillator strength, whereas the second regime arises from pump-induced lattice heating effects primarily associated with a spectral shift of the exciton energy. In addition, vibrational excitation enhances the biexciton emission, which we attribute to a stronger intralayer exciton confinement as well as vibrationally induced exciton detrapping from defect states. Our study provides fundamental insights regarding the impact of organic spacers on excitons in 2DHPs, as well as the excited-state dynamics and vibrational energy dissipation in these structurally diverse materials.

Influence of iron and neodymium doping on ZnSe crystals’ optical properties studied by femtosecond pump-probe spectroscopy

Influence of iron and neodymium doping on ZnSe crystals’ optical properties studied by femtosecond pump-probe spectroscopy

Self-assembling cobalt(II) porphyrin - fullero [60]pyrrolidine triads. Synthesis and spectral properties in the ground and excited state

Meso‑4-Trifluoromethylphenyl substituted cobalt(II)porphin, CoT(CF3P)P, and its coordination 1: 2 complex (triad) with 1-N-methyl-2-(pyridin-4-yl)-3,4-fullero [60]pyrrolidine, (PyC60)2CoT(CF3P)P, were firstly synthesized and the properties of their molecular solutions were studied. The chemical structure of CoT(CF3P)P and triad was fully confirmed by the UV–vis, IR and 1H NMR spectroscopy and mass spectrometry methods. The triad formation mechanism as the two-step equilibrium characterized by equilibrium constant K1 (5.89 ± 1.50) × 104 M−1 and K2 (7.40 ± 1.66) × 105 M−1 was revealed. Using femtosecond pump-probe spectroscopy measurements, the photoinduced electron transfer in the synthesized triad was described. The excited state lifetime of the precursors, CoTPP, CoT(CF3P)P and the charge separated state lifetime of (PyC60)2CoT(CF3P)P compared with unsubstituted (PyC60)2CoTPP were determined. It was established that the CF3 groups in the porphyrin periphery slightly change the CoTPP/CoT(CF3P)P excited state lifetime and the electron transfer rate constant in the correspondent triads.