Pump-probe Spectroscopy Research Articles

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.

Organic and inorganic sublattice coupling in two-dimensional lead halide perovskites

Two-dimensional layered organic-inorganic halide perovskites have successfully spread to diverse optoelectronic applications. Nevertheless, there remain gaps in our understanding of the interactions between organic and inorganic sublattices that form the foundation of their remarkable properties. Here, we examine these interactions using pump-probe spectroscopy and ab initio molecular dynamics simulations. Unlike off-resonant pumping, resonant excitation of the organic sublattice alters both the electronic and lattice degrees of freedom within the inorganic sublattice, indicating the existence of electronic coupling. Theoretical simulations verify that the reduced bandgap is likely due to the enhanced distortion index of the inorganic octahedra. Further evidence of the mechanical coupling between these two sublattices is revealed through the slow heat transfer process, where the resultant lattice tensile strain launches coherent longitudinal acoustic phonons. Our findings explicate the intimate electronic and mechanical couplings between the organic and inorganic sublattices, crucial for tailoring the optoelectronic properties of two-dimensional halide perovskites.

Chirality-Dependent Dynamic Evolution for Trions in Monolayer WS2.

Monolayer transition metal dichalcogenides exhibit valley-dependent excitonic characters with a large binding energy, acting as the building block for future optoelectronic functionalities. Herein, combined with pump-probe ultrafast transient transmission spectroscopy and theoretical simulations, we reveal the chirality-dependent trion dynamics in h-BN encapsulated monolayer tungsten disulfide. By resonantly pumping trions in a single valley and monitoring their temporal evolution, we identify the temperature-dependent competition between two relaxation channels driven by chirality-dependent scattering processes. At room temperature, the phonon-assisted upconversion process predominates, converting excited trions to excitons within the same valley on a sub-picosecond (ps) time scale. As temperature decreases, this process becomes less efficient, while alternative channels, notably valley depolarization process for trions, assume importance, leading to an increase of trion density in the unpumped valley within a ps time scale. Our time-resolved valley-contrast results provide a comprehensive insight into trion dynamics in 2D materials, thereby advancing the development of novel valleytronic devices.

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.

Surface-state-related carrier dynamics of GaAs determined by UV-visible pump-probe terahertz spectroscopy

The surface velocity and the bulk lifetime of photo-excited free carriers in GaAs were measured using an optical-pump and THz-probe time-domain technique. By varying the pump laser photon energy from 1.56 to 4.15 eV, we observe that the surface velocity drops abruptly from 0.7×106 cm/s down to 0.2×106 cm/s at 2.5 eV, while the bulk lifetime remains almost constant. We tentatively explain this step-like behavior of the surface velocity vs the photon energy by a trapping of the free carriers at surface states, whose density of states shows a maximum at 2.5 eV.

Extraordinary Polarization and Thickness Dependences of Photocarrier Dynamics in PdSe2 Ribbons.

Pentagonal palladium diselenide (PdSe2) stands out for its exceptional optoelectronic properties, including high carrier mobility, tunable bandgap, and anisotropic electronic and optical responses. Herein, we systematically investigate photocarrier dynamics in PdSe2 ribbons using polarization-resolved optical pump-probe spectroscopy. In thin PdSe2 ribbons with a semiconductor phase, the photocarrier dynamics are found to be dominated by intraband hot-carrier cooling, interband recombination, and the exciton effect, showing weak crystalline orientation dependences. Conversely, in thick semimetal-phase PdSe2 ribbons, the photocarrier relaxations governed by the electron-optical/acoustic phonon scattering strongly depend on the sample orientation, albeit with a degradation in in-plane anisotropy following hot-carrier cooling. Furthermore, we analyze the correlations between photocarrier dynamics and anisotropic energy dispersions of electronic structures across a wide range in k space, as well as the contributions from the anisotropic electron-phonon couplings. Our study provides crucial insights for developing polarization-sensitive photoelectronic devices based on PdSe2.

Experimental demonstration of attosecond pump–probe spectroscopy with an X-ray free-electron laser

Experimental demonstration of attosecond pump–probe spectroscopy with an X-ray free-electron laser

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.

Study on microscopic origin of spin excitation in TmFeO3 by time-resolved multicolor optical pump-probe spectroscopy

Spin dynamics of TmFeO3, mainly induced by two different mechanisms, were investigated by time-resolved multicolor pump-probe spectroscopy using femtosecond laser pulses. The spin dynamics, caused either by spin-reorientation phase transition or optical polarization-dependent effect, were distinguished by investigating their dependencies on external magnetic field and optical polarization. Spectral-dependent magneto-optic studies of the spin phase transition-induced spin dynamics revealed that laser-induced nonthermal exchange interaction between the electron states of iron (Fe3+) and thulium (Tm3+) ions is crucial for subsequent spin dynamics. This exchange interaction is influenced by the population change of the 4f electron states of Tm3+ ions, making the spin wave generation highly dependent on crystal temperature. However, spectroscopic studies of the polarization-dependent spin dynamics show that they are only related to the 3d electrons of Fe3+ ions, therefore, the spin dynamics appear to be a universal effect over a wide temperature range. Our observation can be further applied to study extended orthoferrite systems with other rare earth atoms.

Photoaquation of cis-[Rh(dppz)(phen)Cl2]Cl complex prospective as potential light-activated anti-cancer agent

The photoactivated drug usage in anti-cancer therapy, the working mechanism of which doesn’t rely on the formation of reactive oxygen species, allows reducing damage to healthy tissue by controlling toxicity. For instance, light-activated Rh(III) complexes show nuclease activity after irradiation with UV and visible light. However, literature analysis shows a lack of descriptions of basic photochemical mechanisms. Here we report the study of cis-[Rh(dppz)(phen)Cl2]Cl (DPPZPHEN, dppz is dipyrido[3,2-a:2′,3′-c]phenazine, phen is 1,10-phenanthroline) photochemistry in water solutions using stationary photolysis, nanosecond laser flash photolysis and ultrafast pump–probe spectroscopy. After the irradiation with 308 nm light, DPPZPHEN undergoes aquation, which results in the substitution of one chloride ligand by a water molecule and leads to the formation of [Rh(dppz)(phen)(H2O)Cl]Cl2. UV–vis spectra of complex and capillary electrophoresis data were collected and discussed. Laser flash photolysis (355 nm) demonstrates intermediate absorption attributed to the lowest electronic excited state (triplet) of the initial complex. The study of primary photophysical processes showed a rather complicated behavior of transient absorption, which could be described by a set of four exponential functions. The early photophysical processes were described by the scheme including the formation of two excited states of different natures, namely a dppz-based IL state and an LMCT state.

Compact realization of all-attosecond pump-probe spectroscopy.

The ability to perform attosecond-pump attosecond-probe spectroscopy (APAPS) is a longstanding goal in ultrafast science. While first pioneering experiments demonstrated the feasibility of APAPS, the low repetition rates (10 to 120 Hz) and the large footprints of existing setups have so far hindered the widespread exploitation of APAPS. Here, we demonstrate two-color APAPS using a commercial laser system at 1 kHz, straightforward post-compression in a hollow-core fiber, and a compact high-harmonic generation (HHG) setup. The latter enables the generation of intense extreme-ultraviolet (XUV) pulses by using an out-of-focus HHG geometry and by exploiting a transient blueshift of the driving laser in the HHG medium. Near-isolated attosecond pulses are generated, as demonstrated by one-color and two-color XUV-pump XUV-probe experiments. Our concept allows selective pumping and probing on extremely short timescales in many laboratories and permits investigations of fundamental processes that are not accessible by other pump-probe techniques.

Regulation of Hot Electrons Transport Achieved through Controlled Electron-Phonon Coupling in Metallic Heterostructures.

The electron-phonon (e-ph) interactions are pivotal in shaping the electrical and thermal properties, and in particular, determining the carrier dynamics and transport behaviors in optoelectronic devices. By employing pump-probe spectroscopy and ultrafast microscopy, the consequential role of e-ph coupling strength in the spatiotemporal evolution of hot electrons is elucidated. Thermal transport across the metallic interface is controlled to regulate effective e-ph coupling factor Geff in Au and Au/Cr heterostructure, and their impact on nonequilibrium transport of hot electrons is examined. Via the modulation of buried Cr thickness, a strong correlation between Geff and the diffusive behavior of hot electrons is found. By enhancing Geff through the regulation of thermal transport across interface, there is a significant reduction in e-ph thermalization time, the maximum diffusion length of hot electrons, and lattice heated area which are extracted from the spatiotemporal evolution profiles. Therefore, the increased Geff significantly weakens the diffusion of hot electrons and promotes heat relaxation of electron subsystems in both time and space. These insights propose a robust framework for spatiotemporal investigations of G impact on hot electron diffusion, underscoring its significance in the rational design of advanced optoelectronic devices with high efficiency.

Signatures of Fractional Statistics in Nonlinear Pump-Probe Spectroscopy.

We show that the presence of anyons in the excitation spectrum of a two-dimensional system can be inferred from nonlinear spectroscopic quantities. In particular, we consider pump-probe spectroscopy, where a sample is irradiated by two light pulses with an adjustable time delay between them. The relevant response coefficient exhibits a universal form that originates from the statistical phase acquired when anyons created by the first pulse braid around those created by the second. This behavior is shown to be qualitatively unchanged by nonuniversal physics including nonstatistical interactions and small nonzero temperatures. In magnetic systems, the signal of interest can be measured using currently available terahertz-domain probes, highlighting the potential usefulness of nonlinear spectroscopic techniques in the search for quantum spin liquids.

Anomalous thermal relaxation and pump-probe spectroscopy of two-dimensional topologically ordered systems

We study the behavior of linear and nonlinear spectroscopic quantities in two-dimensional topologically ordered systems, which host anyonic excitations exhibiting fractional statistics. We highlight the role that braiding phases between anyons have on the dynamics of such quasiparticles, which as we show dictates the behavior of both linear response coefficients at finite temperatures, as well as nonlinear pump-probe response coefficients. These quantities, which act as probes of temporal correlations in the system, are shown to obey distinctive universal forms at sufficiently long timescales. As well as providing an experimentally measurable fingerprint of anyonic statistics, the universal behavior that we find also demonstrates anomalously fast thermal relaxation: correlation functions decay as a “squished exponential” C(t)∼exp(−[t/τ]3/2) at long times. We attribute this unusual asymptotic form to the nonlocal nature of interactions between anyons, which allows relaxation to occur much faster than in systems with quasiparticles interacting via local, nonstatistical interactions. While our results apply to any Abelian or non-Abelian topological phase in two-dimensions, we discuss in particular the implications for candidate quantum spin liquid materials, wherein the relevant quantities can be measured using pre-existing time-resolved terahertz-domain spectroscopic techniques. Published by the American Physical Society 2024

Tunneling-Driven Marcus-Inverted Triplet Energy Transfer in a Two-Dimensional Perovskite.

Quantum tunneling, a phenomenon that allows particles to pass through potential barriers, can play a critical role in energy transfer processes. Here, we demonstrate that the proper design of organic-inorganic interfaces in two-dimensional (2D) hybrid perovskites allows for efficient triplet energy transfer (TET), where quantum tunneling of the excitons is the key driving force. By employing temperature-dependent and time-resolved photoluminescence and pump-probe spectroscopy techniques, we establish that triplet excitons can transfer from the inorganic lead-iodide sublattices to the pyrene ligands with rapid and weakly temperature-dependent characteristic times of approximately 50 ps. The energy transfer rates obtained based on the Marcus theory and first-principles calculations show good agreement with the experiments, indicating that the efficient tunneling of triplet excitons within the Marcus-inverted regime is facilitated by high-frequency molecular vibrations. These findings offer valuable insights into how one can effectively manipulate the energy landscape in 2D hybrid perovskites for energy transfer and the creation of diverse excitonic states.

Understanding the [NiFe] Hydrogenase Active Site Environment through Ultrafast Infrared and 2D-IR Spectroscopy of the Subsite Analogue K[CpFe(CO)(CN)2] in Polar and Protic Solvents.

The [CpFe(CO)(CN)2]- unit is an excellent structural model for the Fe(CO)(CN)2 moiety of the active site found in [NiFe] hydrogenases. Ultrafast infrared (IR) pump-probe and 2D-IR spectroscopy have been used to study K[CpFe(CO)(CN)2] (M1) in a range of protic and polar solvents and as a dry film. Measurements of anharmonicity, intermode vibrational coupling strength, vibrational relaxation time, and solvation dynamics of the CO and CN stretching modes of M1 in H2O, D2O, methanol, dimethyl sulfoxide, and acetonitrile reveal that H-bonding to the CN ligands plays an important role in defining the spectroscopic characteristics and relaxation dynamics of the Fe(CO)(CN)2 unit. Comparisons of the spectroscopic and dynamic data obtained for M1 in solution and in a dry film with those obtained for the enzyme led to the conclusion that the protein backbone forms an important part of the bimetallic active site environment via secondary coordination sphere interactions.

Transient responses of double core-holes generation in all-attosecond pump-probe spectroscopy

Double core-holes (DCHs) show remarkable and sensitive effects for understanding electron correlations and coherence. With advanced modulation of x-ray free-electron laser (XFEL) facility, we propose the forthcoming all-attosecond XFEL pump-probe spectroscopy can decipher the hidden photon-initiated dynamics of DCHs. The benchmark case of neon is investigated, and norm-nonconserving Monte-Carlo wavefunction method simulates non-Hermitian dynamics among vast states, which shows superiority in efficiency and reliability. In our scheme, population transfer to DCHs is sequentially irradiated by pump and probe laser. By varying time delay, Stark shifts and quantum path interference of resonant lines sensitively emerge at specific interval of two pulses. These ubiquitous multi-channel effects are also observed in phase-fluctuating pulses, derived from extra phases of impulsive Raman processes by pump laser. Non-perturbation absorption/emission verifies the uniquely interchangeable role of two pules in higher intensity. Our results reveal sensitive and robust responses on pulse parameters, which show potential capacity for XFEL attosecond pulse diagnosis and further attosecond-timescale chemical analysis.

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.

Coherent and Incoherent Ultrafast Dynamics in Colloidal Gold Nanorods.

The study of the mechanisms that control the ultrafast dynamics in gold nanoparticles is gaining more attention, as these nanomaterials can be used to create nanoarchitectures with outstanding optical properties. Here pump-probe and two-dimensional electronic spectroscopy have been synergistically employed to investigate the early ultrafast femtosecond processes following photoexcitation in colloidal gold nanorods with low aspect ratio. Complementary insights into the coherent plasmonic dynamics at the femtosecond time scale and incoherent hot electron dynamics over picosecond time scales have been obtained, including important information on the different sensitivity to the pump fluence of the longitudinal and transverse plasmons and their different contributions to the photoinduced broadening and shift.

In situ generation and reaction of a sub-picosecond electron pulse: ultrafast broadband spectroscopy.

A sub-picosecond resolved broadband transient absorption spectrometer for in situ generation and study of ultrafast reaction of short pulse electrons in water has been reported. A femtosecond near infrared (NIR) laser driven multiphoton ionization of water was used for the in situ generation of an ultra-short electron pulse in aqueous media. The dynamics of such electrons have been investigated using a broadband pump-probe spectrometer with a temporal resolution of sub-picosecond. The formation of the pre-hydrated electron having absorption in the NIR region and its subsequent solvation process leading to the formation of the hydrated electron has been monitored in real time using pump-probe spectroscopy. As a proof of concept, a reaction of pre-hydrated electrons and hydrated electrons with a highly oxidizing agent, methyl viologen, has been carried out. The competition of the reaction with methyl viologen and solvent relaxation of the pre-hydrated electron has been demonstrated by broadband ultrafast spectroscopy. Our results show that the reactivity of pre-hydrated electrons with methyl viologen is almost two orders of magnitude higher as compared to the hydrated electrons. Unlike complicated laser driven accelerators, the present table-top setup for the generation of an in situ ultrashort electron pulse and its reaction with different classes of molecules, especially biomolecules, will help us understand the early events of radiation-induced processes under reductive stress.