Ultrafast Pump-probe Spectroscopy Research Articles

Photophysics and photochemistry of (n-Bu4N)2[Pt(NO3)6] in acetonitrile: ultrafast pump-probe spectroscopy and quantum chemical insight.

The ultrafast processes caused by photoexcitation of (n-Bu4N)2[Pt(NO3)6] complex in acetonitrile were studied by means of transient absorption (TA) pump-probe spectroscopy and verified by quantum chemical calculations. The primary photochemical process was found to be an inner-sphere electron transfer followed by an escape of an •NO3 radical to the bulk solution. The reaction occurs via the dissociative triplet excited LMCT state of the initial complex. Based on the experimental data and quantum chemical calculations, the mechanism of ultrafast photophysical and photochemical processes is proposed.

Controlling friction energy dissipation by ultrafast interlayer electron-phonon coupling in WS2/graphene heterostructures

Electrons and phonons are regarded as the microscopic carriers of friction energy dissipation and their coupling is a typical dissipation mode. However, due to the lack of ultrafast detection technic, the friction mechanism about electron-phonon coupling remains unexplained. Here, using high resolution non-contact atomic force microscopy and ultrafast pump-probe spectroscopy, we find that interlayer electron-phonon coupling dissipation channel in WS2/graphene heterostructures can be enhanced by defects and the electron-phonon scattering time is accelerated from 0.62ps to 0.27ps. The enhanced electron-phonon coupling leads to significant energy dissipation. We further quantitatively model the friction with dissipation rate to control the friction energy dissipation by ultrafast interlayer electron-phonon coupling. This work provides a new way to understand the mechanism of electron-phonon coupling in friction.

Symmetry Breaking Charge Separation in Far-Red Absorbing Bisstyryl-Bodipy Dimers

Symmetry breaking charge transfer is one of the important photo-events occurring in photosynthetic reaction centers that is responsible for initiating electron transfer leading to a long-lived charge-separated state and has been successfully employed in light-to-electricity converting optoelectronic devices. Here, we report the synthesis of far-red absorbing and emitting BODIPY-dimer to undergo symmetry-breaking charge transfer leading to charge-separated states of appreciable lifetimes in polar solvents. Compared to its monomer analog, both steady-state and time-resolved fluorescence originating from the S1 state of the dimer revealed quenching which increased with an increase in solvent polarity. The electrostatic potential map from DFT and the time-dependent DFT calculations suggested the existence of a quadrupolar type charge transfer state in polar solvents, and the singlet excited state to be involved in the charge separation process. The electrochemically determined redox gap to be smaller than the energy of the S1 state supporting thermodynamic feasibility of the envisioned symmetry-breaking charge transfer and separation. The spectrum of the charge-separated state arrived from spectroelectrochemical studies, revealing diagnostic peaks helpful for transient spectral interpretation. Finally, ultrafast transient pump-probe spectroscopy provided conclusive evidence of diabatic charge separation in polar solvents by far-red pulsed laser light irradiation. The measured lifetime of the final charge-separated states was found to be 165 ps in dichlorobenzene, 140 ps in benzonitrile, and 43 ps in dimethyl sulfoxide, revealing their significance in light energy harvesting, especially from the less-explored far-red region.

Anisotropic phonon dynamics in Dirac semimetal PtTe2 thin films enabled by helicity-dependent ultrafast light excitation

Coherent phonons have aroused considerable attention in condensed matter physics owing to their extraordinary capacity of reflecting and controlling the physical properties of matter. However, the investigation on the interaction between coherent phonons and other microscopic particles on the ultrafast timescale within topological systems continues to be an active and unresolved area. Here, we show the energy transfer of coherent optical phonons (COP) in Dirac semimetal PtTe2 thin films using ultrafast optical pump-probe spectroscopy. Specifically, the helicity-dependent light-driven anisotropic COP signals disclose their direct connection with the light-excited anisotropic spin-polarized electrons via an angular momentum transfer. Furthermore, we observe the notable decreases in the COP oscillation frequency and the decay rate with increasing temperatures due to the anharmonic phonon-phonon scattering and electron-phonon scattering in the COP dissipation process, respectively. Our work paves the way for uncovering the coherent phonons in Dirac semimetals for the potential applications in optoelectronics and opto-spintronics.

Manipulating Ferroelectric Polarization and Spin Polarization of 2D CuInP2S6 Crystals for Photocatalytic CO2 Reduction.

Manipulating electronic polarizations such as ferroelectric or spin polarizations has recently emerged as an effective strategy for enhancing the efficiency of photocatalytic reactions. This study demonstrates the control of electronic polarizations modulated by ferroelectric and magnetic approaches within a two-dimensional (2D) layered crystal of copper indium thiophosphate (CuInP2S6) to boost the photocatalytic reduction of CO2. We investigate the substantial influence of ferroelectric polarization on the photocatalytic CO2 reduction efficiency, utilizing the ferroelectric-paraelectric phase transition and polarization alignment through electrical poling. Additionally, we explore enhancing the CO2 reduction efficiency by harnessing spin electrons through the synergistic introduction of sulfur vacancies and applying a magnetic field. Several advanced characterization techniques, including piezoresponse force microscopy, ultrafast pump-probe spectroscopy, in situ X-ray absorption spectroscopy, and in situ diffuse reflectance infrared Fourier transformed spectroscopy, are performed to unveil the underlying mechanism of the enhanced photocatalytic CO2 reduction. These findings pave the way for manipulating electronic polarizations regulated through ferroelectric or magnetic modulations in 2D layered materials to advance the efficiency of photocatalytic CO2 reduction.

Ultrafast Dynamics of Bloch Surface Wave Polaritons in Large-Area 2D Semiconductor Monolayers at Room Temperature.

The dynamics of strongly coupled polariton systems integrated with 2D transition metal dichalcogenides (TMDs) is key to enabling efficient coherent processes and achieving high-performance TMD-based polaritonic devices, such as ultralow-threshold polariton lasers and ultrafast optical switches. However, there has been a lack of a comprehensive understanding of the excited state dynamics in TMD-based polariton systems. In this work, ultrafast pump-probe optical spectroscopy is used to investigate the room temperature dynamics of the polariton systems consisting of TMD monolayer excitons strongly coupled with Bloch surface waves (BSWs) supported by all-dielectric photonic structures. The transient response is found for both above-exciton energy pumping and polariton-resonant pumping. The excited state population and ultrafast coherent coupling of the exciton reservoir and lower polariton (LP) branch are observed for resonant pumping. Moreover, it is found that the transient response of the LP first decays on a short-time scale of 0.15-0.25ps compared to the calculated intrinsic lifetime of 0.11-0.20ps, and is followed by a longer decay (>100ps) due to the dynamical evolution of the exciton reservoir. The results provide a fundamental understanding of the dynamics of TMD-based polariton systems while showing the potential for achieving efficient coherent optical processes for device applications.

Unraveling Defect-Mediated Enhancement of Transient Photoconductivity and Slower Carrier's Mobility Decay in Cu-Doped Cs2AgBiBr6 Nanocrystals Using Ultrafast Pump-Probe Spectroscopy.

Lead-free double perovskite nanocrystals (A2B'(III)B″(I)X6 NCs) address the instability and toxicity concerns of lead-based counterparts, but their device performance is limited by subpar absorption and unexplored carrier dynamics. Impurity ion doping offers a route to tune electrical conductivity and charge carrier transport. Herein, we synthesized Cu-doped Cs2AgBiBr6 (CABB) nanocrystals using a hot-injection approach and investigated the charge carrier's dynamics through ultrafast pump-probe spectroscopy. Copper introduction into the CABB lattice enhanced absorption in the near-infrared region and introduced sub-band gap defect states in CABB NCs. The transient absorption study revealed a faster bleach decay with increased copper doping, as a result of charge transfer from the conduction band to copper defect states. Also, an optical pump terahertz probe study displays higher photoconductivity and mobility in Cu-doped CABB NCs. Slower mobility decay in Cu-doped systems was attributed to the charge carrier's entrapment at the defect state. These findings suggest that copper-doped CABB is a superior contender for optoelectronic applications over conventional CABB.

Vibrational coherences in half-broadband 2D electronic spectroscopy: Spectral filtering to identify excited state displacements.

Vibrational coherences in ultrafast pump-probe (PP) and 2D electronic spectroscopy (2DES) provide insights into the excited state dynamics of molecules. Femtosecond coherence spectra and 2D beat maps yield information about displacements of excited state surfaces for key vibrational modes. Half-broadband 2DES uses a PP configuration with a white light continuum probe to extend the detection range and resolve vibrational coherences in the excited state absorption (ESA). However, the interpretation of these spectra is difficult as they are strongly dependent on the spectrum of the pump laser and the relative displacement of the excited states along the vibrational coordinates. We demonstrate the impact of these convoluting factors for a model based upon cresyl violet. A careful consideration of the position of the pump spectrum can be a powerful tool in resolving the ESA coherences to gain insights into excited state displacements. This paper also highlights the need for caution in considering the spectral window of the pulse when interpreting these spectra.

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.

Symmetry breaking charge transfer leading to charge separation in a far-red absorbing bisstyryl-BODIPY dimer.

Symmetry breaking charge transfer is one of the important photo-events occurring in photosynthetic reaction centers that is responsible for initiating electron transfer leading to a long-lived charge-separated state and has been successfully employed in light-to-electricity converting optoelectronic devices. In the present study, we report a newly synthesized, far-red absorbing and emitting BODIPY-dimer to undergo symmetry-breaking charge transfer leading to charge-separated states of appreciable lifetimes in polar solvents. Compared to its monomer analog, both steady-state and time-resolved fluorescence originating from the S1 state of the dimer revealed quenching which increased with an increase in solvent polarity. The electrostatic potential map from DFT and the time-dependent DFT calculations suggested the existence of a quadrupolar type charge transfer state in polar solvents, and the singlet excited state to be involved in the charge separation process. The electrochemically determined redox gap being smaller than the energy of the S1 state supported the thermodynamic feasibility of the envisioned symmetry-breaking charge transfer and separation. The spectrum of the charge-separated state arrived from spectroelectrochemical studies, revealing diagnostic peaks helpful for transient spectral interpretation. Finally, ultrafast transient pump-probe spectroscopy provided conclusive evidence of diabatic charge separation in polar solvents by far-red pulsed laser light irradiation. The measured lifetime of the final charge-separated states was found to be 165 ps in dichlorobenzene, 140 ps in benzonitrile, and 43 ps in dimethyl sulfoxide, revealing their significance in light energy harvesting, especially from the less-explored far-red region.

Exploring charge transfer mechanisms and optical properties in vdW heterostructures of MoS2 and Bi2Se3 at nanoscale regime

We report here the two-dimensional layered material of MoS2/Bi2Se3 vdW heterostructures formed by ultrasonication of different concentrations of exfoliated MoS2 and Bi2Se3 nanosheets. The vdW heterostructures show unique optical characteristics compared to individual exfoliated nanosheets. The enhanced lifetime of heterostructures explained the charge transfer with increasing efficacy for producing optoelectronic devices. Raman spectroscopy confirms the presence of intrinsic Raman active modes of Bi2Se3, MoS2, and respective modes of vdW heterostructures. TEM images show characteristic lattice planes in both materials and clear overlapping regimes, confirming successful heterojunction formation. Further, Zeta potential confirms the enhanced stability of the heterostructures formed while the significant PL quenching, strongly suggests the presence of charge transfer processes within the heterostructures. Ultrafast pump-probe spectroscopy further confirms the non-linear charge transfer and relaxation mechanism of the heterostructures. We employed Surface Xplorer and Glotaran software for model fitting and Glotaran's global fitting revealed unresolved charge carrier dynamics.

Tuning the Optical Properties Through Hydrogen Bond-assisted H-aggregate Formation: The ODIN Case.

The current work focuses on the investigation of two functionalized naphthyridine derivatives, namely ODIN-EtPh and ODIN-But, to gain insights into the hydrogen bond-assisted H-aggregate formation and its impact on the optical properties of ODIN molecules. By employing a combination of X-ray and electron crystallography, absorption and emission spectroscopy, time resolved fluorescence and ultrafast pump-probe spectroscopy (visible and infrared) we unravel the correlation between the structure and light-matter response, with a particular emphasis on the influence of the polarity of the surrounding environment. Our experimental results and simulations confirm that in polar and good hydrogen-bond acceptor solvents (DMSO), the formation of dimers for ODIN derivatives is strongly inhibited. The presence of a phenyl group linked to the ureidic unit favors the folding of ODIN derivatives (forming an intramolecular hydrogen bond) leading to the stabilization of a charge-transfer excited state which almost completely quenches its fluorescence emission. In solvents with a poor aptitude for forming hydrogen bonds, the formation of dimers is favored and gives rise to H aggregates, with a consequent considerable reduction in the fluorescence emission. The urea-bound phenyl group furtherly stabilizes the dimers in chloroform.

Ultrafast pump-probe spectroscopy via chirped-pulse up-conversion with dispersion compensation.

In this study, ultrafast transient signals were detected on a single-shot basis using chirped-pulse up-conversion spectroscopy with dispersion compensation. Unlike in the conventional time-encoding technique using chirped pulses, distortion of the ultrafast waveform was reduced by applying dispersion compensation to the chirped probe pulses and using sum-frequency generation with the chirped readout pulses. The method was applied to terahertz time-domain spectroscopy and near-infrared pump-probe spectroscopy, providing ultrafast observations with an improved temporal resolution comparable to the transform-limited pulse durations. Terahertz waveforms, Kerr rotation signals, and phonon-polariton oscillations were measured accurately with no significant waveform distortion, thereby showing the proposed scheme to be promising for single-shot pump-probe spectroscopy in a wide range of spectroscopic applications.

Critical and controversial issues pertaining to the growth and properties of Cu2O in the context of energy conversion

Cu2O has been deposited on m-, r-, and a-Al2O3 by reactive sputtering of Cu using Ar with different contents of O2 followed by annealing under carefully optimized conditions at 500 °C under Ar:H2 in order to prevent the oxidation and reduction of the Cu2O layers, which have a cubic crystal structure and are bulk-relaxed. We find that the content of O2 influences the structural and optical properties of the Cu2O layers that exhibited a detailed spectral structure and distinct peaks at 2.75, 2.54, and 2.17 eV corresponding to the indigo, blue, and yellow direct gap transitions of Cu2O as observed by ultrafast pump–probe spectroscopy at room temperature. However, we also observed a transition at 1.8 eV that is related to the occurrence of states ∼0.4 eV below the conduction band minimum of Cu2O. We discuss the controversial origin of these states, which are usually attributed to donor-like oxygen vacancy states, and suggest that the origin of these states may be related to traps at the interfaces of CuO/Cu2O nanostructures, which is important in the context of energy conversion pertaining to solar cells and photocatalysis.

Unveiling Solvation Dynamics of Excited and Ground States via Ultrafast Pump-Dump-Probe Spectroscopy.

The conventional ultrafast pump-probe spectroscopy has primarily focused on examining the formation and decay of the excited state intermediates, but it is very difficult to detect those intermediates while the formation is slow and dissipation is much fast because of the limited concentration during the intrinsic photocycle. To address this issue, a multipulse ultrafast pump-dump-probe spectroscopy was employed to generate and probe the short-lived ground state intermediates (GSIs) in an electronic push-pull pyrene derivative (EPP). This particular derivative undergoes planarized intramolecular charge transfer (PICT) in the excited state upon initial femtosecond pulse excitation. After applying the dump pulse once the PICT was formed, the blue-shifted transient absorption GSIs with the ground state dynamics of the structure recovery was directly observed. It is found that GSIs undergo slower reorganization than the PICT formation in the excited state of EPP due to the solvation effect with different dipole moments of ground states and excited states. These findings provide a comprehensive understanding of the full photocycle dynamics of both the ground and excited states, shedding light on the presence of hidden ground state behaviors.

Unraveling the Hybridization Process in CeAgSb2 Kondo Lattice

We present a comprehensive investigation utilizing ultrafast optical pump-probe spectroscopy to elucidate the intricate quasiparticle dynamics in the CeAgSb2 single crystal. Through our experimental endeavors, a nuanced two-phase evolution in the hybridization phenomena linking localized f moments and conduction electrons has been unveiled. This intricate process is manifest in two distinct manifestations: firstly, the discernible manifestation of hybridization fluctuations spanning the temperature range of approximately 150 K (denoted as T†) down to approximately 65 K (referred to as T*); secondly, the notable emergence of a collective hybridization phenomenon below the critical temperature, T*, as indicated by the onset of an indirect gap in the electronic structure. These discerning observations provide invaluable insights into the interplay of electronic configurations as a function of temperature in CeAgSb2, shedding light on its unique properties and behaviors.

Ultrafast damage dynamics and ablation mechanism of GaSe induced by femtosecond laser irradiation

With the development of high-power infrared lasers and optical devices based on GaSe, more attention has been paid to its optical damage under laser irradiation. Understanding the interactions at the surface of GaSe during femtosecond laser irradiation is essential for its applications as infrared nonlinear optical and optoelectronic devices. Here, ultrafast damage dynamic process and ablation mechanism of GaSe under femtosecond laser irradiation are studied. Two types of damage/ablation mechanisms are proposed according to two distinct types of damaged morphologies and damaged products, and further confirmed by ultrafast pump–probe spectroscopy. At lower fluences, the laser-induced damage of GaSe can be attributed to the formation of new products by chemical bonds broken and phase transitions, changing the stoichiometry and spectra while barely destroy surface morphologies. At higher fluences, surface plasma is formed with massive hot free electrons in the conduction band from the multi-photon ionization and avalanche ionization. The plasma heats the surface and forms shock wave, which removes the surface layer by vaporization, causing a damage pit on the surface. Our results gain insight into damage dynamics of GaSe under laser irradiation, which can help to have a deeper comprehension of the laser-materials interaction.

Long-Range Interface Effects in Room Temperature Ionic Liquids: Vibrational Lifetime Studies of Thin Films.

Interface effects in the room temperature ionic liquids (RTILs) 1-butyl-3-methylimidazolium tetrafluoroborate (BmimBF4) and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BmimNTf2) were investigated using ultrafast infrared polarization selective pump-probe (PSPP) spectroscopy. The CN stretch mode of SCN- dissolved in the RTILs was used as the vibrational probe. The vibrational lifetime of the SCN- was the experimental observable. Quite similar single SCN- lifetimes were observed: 59.5 ± 0.4 ps in bulk BmimBF4 and 56.4 ± 0.4 ps in bulk BmimNTf2. Thin films of both RTILs with thicknesses in the range of 15-300 nm were prepared by spin coating on functionalized substrates. PSPP experiments were performed in a small-incidence reflection geometry. In the thin films, a second, shorter lifetime was observed in addition to the bulk lifetime, with the amplitude of the shorter lifetime increasing with decreasing film thickness. By modeling the thickness dependence of the lifetime amplitudes, the correlation length of the interface effect (constant for exponential falloff of the influence of the interface) was determined to be 44.6 ± 0.6 nm for BmimBF4 and 48.3 ± 2.2 nm for BmimNTf2. The values for the shorter film lifetimes were 12.6 ± 0.1 ps for BmimBF4 and 20.2 ± 0.6 ps for BmimNTf2; the substantial differences from the bulk lifetimes showed that some of the SCN- anions near the interface experience an environment distinct from that of the bulk. It was also found that for the BmimNTf2 sample only, some of the SCN- anions reside in the surface functionalized layer with two distinct environments having distinct lifetimes.

Cover Feature: Symmetrically Functionalized Copper and Silver Corrole‐Bis‐Tetracyanobutadiene Push‐Pull Conjugates: Efficient Population of Triplet States via Charge Transfer (Chem. Eur. J. 41/2023)

Chemistry–art–culture combo: Rangoli, an ancient art from the Indian subcontinent, creates designs on the floor by using dry powders. A rangoli of the structure of the investigated compound is depicted here to link chemistry to art to culture. An efficient population of triplet excited states via the intermediate charge-transfer state formed as a function of excitation wavelength is demonstrated by using ultrafast pump–probe spectroscopy in these symmetrically functionalized push–pull systems. More information can be found in the Research Article by M. Sankar, F. D'Souza, and co-workers (DOI: 10.1002/chem.202301341). Artists: I. Yadav, N. Rana, R. Jangra and S. Rathi.

Twisted chiral superconductivity in photodoped frustrated Mott insulators

Recent advances in ultrafast pump-probe spectroscopy provide access to hidden phases of correlated matter, including light-induced superconducting states, but the theoretical understanding of these nonequilibrium phases remains limited. Here we report how a new type of chiral superconducting phase can be stabilized in photodoped frustrated Mott insulators. The metastable phase features a spatially varying order parameter with a $120^\circ$ phase twist which breaks both time-reversal and inversion symmetry. Under an external electric pulse, the $120^\circ$ chiral superconducting state can exhibit a second-order supercurrent perpendicular to the field in addition to a first-order parallel response, similar to a nonlinear anomalous Hall effect. This phase can be tuned by artificial gauge fields when the system is dressed by high-frequency periodic driving. The mechanism revealed in this study applies to Mott insulators on various frustrated lattices and the hidden superconducting phase can be realized in both cold-atom quantum simulators and correlated solids.