Search

Nickel (II) oxide, NiO, is a wide band gap Mott insulator characterized by strong Coulomb repulsion between d-electrons and displays antiferromagnetic order at room temperature. NiO has gained attention in recent years as a very promising candidate for applications in a broad set of areas, including chemistry and metallurgy to spintronics and energy harvesting. Here, we report on the fabrication of polycrystalline NiO using spray-pyrolysis technique, which is a deposition technique able to produce quite uniform films of pure and crystalline materials without the need of high vacuum or inert atmospheres. The composition and structure of the NiO thin films were then studied using x-ray diffraction, and atomic force and scanning electron microscopies (SEM). The phononic and magnonic properties of the NiO thin films were also studied via Raman spectroscopy, and the ultrafast electron dynamics by using optical pump probe spectroscopy. We found that the NiO samples display the same phonon and magnon excitations expected for single crystal NiO at room temperature, and that electron dynamics in our system is like those of previously reported NiO mono- and polycrystalline systems synthesized using different techniques. These results prove that spray-pyrolysis can be used as affordable and large-scale fabrication technique to synthesize strongly correlated materials for a large set of applications. [ABSTRACT FROM AUTHOR]

Perylene diimide (PDI) dimers and higher aggregates are key components in organic molecular photonics and photovoltaic devices, supporting singlet fission and symmetry breaking charge separation. Detailed understanding of their excited states is thus important. This has proven challenging because interchromophoric coupling is a strong function of dimer architecture. Recently, a macrocyclic PDI dimer was reported in which excitonic coupling could be turned on and off simply by changing the solvent. This presents a useful case where coupling is modified without synthetic changes to tune supramolecular structure. Here we present a detailed study of solvent dependent excited state dynamics in this dimer by means of coherent multidimensional spectroscopy. Spectral analysis resolves the different coupling strengths, which are consistent with solvent dependent changes in dimer conformation. The strongly coupled conformer forms an excimer within 300 fs. The low‐frequency Raman active modes recovered from two‐dimensional electronic spectra reveal frequencies characteristic of exciton coupling. These are assigned to modes modulating the coupling from the corresponding DFT calculations. Further analysis reveals a time dependent frequency during excimer formation. Analysis of two‐dimensional "beatmaps" reveals features in the coupled dimer which are not predicted by the displaced harmonic oscillator model and are assigned to vibronic coupling. [ABSTRACT FROM AUTHOR]

Titanium nitride (TiN) has recently gained considerable interest because of its remarkable plasmonic properties and for its strong electron–phonon (e–ph) coupling, leading to extremely fast (<100 fs) electron‐lattice cooling. Here, the generation of coherent phonons in TiN films is reported, along with their real‐time detection by means of broadband transient reflection spectroscopy with sub‐15‐fs temporal resolution. The measurements show damped oscillations, superimposed to excited state electronic decay. A coherent vibrational mode is revealed, with ≈10 THz frequency ascribed to defect‐activated normal modes, consistent with spontaneous Raman scattering data, and a dephasing time of ≈250 fs. Two π‐phase flips are also observed located at photon energies corresponding to interband optical transitions (at 3.2 and 2.5 eV), ascribed to selective coupling of the vibrational mode to these transitions; the energy modulation induced by the vibrational coherence is evaluated. It is shown that the displacive excitation of coherent phonons model describes the coherent response in terms of temporal behavior and of spectral amplitude profile. Overall, a comprehensive and detailed analysis of coherent phonons in TiN films, so far undected, is provided and relevant information on TiN photo‐physical properties, potentially useful for its applications, is given. [ABSTRACT FROM AUTHOR]

Artificial photocatalytic energy conversion is a very interesting strategy to solve energy crises and environmental problems by directly collecting solar energy, but low photocatalytic conversion efficiency is a bottleneck that restricts the practical application of photocatalytic reactions. The key issue is that the photo-generated charge separation process spans a huge spatio-temporal scale from femtoseconds to seconds, and involves complex physical processes from microscopic atoms to macroscopic materials. Femtosecond transient absorption (fs-TA) spectroscopy is a powerful tool for studying electron transfer paths in photogenerated carrier dynamics of photocatalysts. By extracting the attenuation characteristics of the spectra, the quenching path and lifetimes of carriers can be simulated on femtosecond and picosecond time scales. This paper introduces the principle of transient absorption, typical dynamic processes and the application of femtosecond transient absorption spectroscopy in photocatalysis, and summarizes the bottlenecks faced by ultrafast spectroscopy in photocatalytic applications, as well as future research directions and solutions. This will provide inspiration for understanding the charge transfer mechanism of photocatalytic processes. [ABSTRACT FROM AUTHOR]

The ring-like peripheral light-harvesting complex 2 (LH2) expressed by many phototrophic purple bacteria is a popular model system in biological light-harvesting research due to its robustness, small size, and known crystal structure. Furthermore, the availability of structural variants with distinct electronic structures and optical properties has made this group of light harvesters an attractive testing ground for studies of structure–function relationships in biological systems. LH2 is one of several pigment-protein complexes for which a link between functionality and effects such as excitonic coherence and vibronic coupling has been proposed. While a direct connection has not yet been demonstrated, many such interactions are highly sensitive to resonance conditions, and a dependence of intra-complex dynamics on detailed electronic structure might be expected. To gauge the sensitivity of energy-level structure and relaxation dynamics to naturally occurring structural changes, we compare the photo-induced dynamics in two structurally distinct LH2 variants. Using polarization-controlled 2D electronic spectroscopy at cryogenic temperatures, we directly access information on dynamic and static disorder in the complexes. The simultaneous optimal spectral and temporal resolution of these experiments further allows us to characterize the ultrafast energy relaxation, including exciton transport within the complexes. Despite the variations in PPC molecular structure manifesting as clear differences in electronic structure and disorder, the energy-transport and—relaxation dynamics remain remarkably similar. This indicates that the light-harvesting functionality of purple bacteria within a single LH2 complex is highly robust to structural perturbations and likely does not rely on finely tuned electronic- or electron-vibrational resonance conditions. [ABSTRACT FROM AUTHOR]

In this work, we synthesize a series of push–pull compounds bearing naphthalimide as the electron acceptor and tetraphenylethylene (TPE)/triphenylamine (TPA)/phenothiazine (PTZ) as the electron rich/electron donor units. These moieties are arranged in highly conjugated quadrupolar structures. The structure–property relationships are investigated through a joint experimental time–resolved spectroscopic and computational TD–DFT study. The femtosecond transient absorption and fluorescence up–conversion experiments reveal ultrafast photoinduced intramolecular charge transfer. This is likely the key factor leading to efficient spin–orbit CT–induced intersystem crossing for the TPA– and PTZ–derivatives as well as to small singlet–to–triplet energy gap. Consequently, evidence for a delayed fluorescence component is found together with the main prompt emission in the fluorescence kinetics both in solution and in thin film. The weight of the Thermally Activated Delayed Fluorescence (TADF) is greatly enhanced when these fluorophores are used as guests in solid–state host matrices. TADF is interestingly revealed in the orange–red region of the visible. Such long wavelength emission is here observed with surprisingly large fluorescence quantum yields, thanks to the conjugation enhancement achieved in these newly synthesized structures relative to previous studies. Our findings may be thus promising for the future development of efficient third generation TADF–based OLEDs. [ABSTRACT FROM AUTHOR]

Layered materials exhibit different electronic and phonon properties along in-plane and out-of-plane directions; existing studies focus on their in-plane behaviors, and the influence of such anisotropies on the dynamics of photocarriers and phonons is unknown. Here, we fabricate layered PdSe2 crystals with flat edge surfaces and compare the time-resolved ultrafast spectroscopies on their basal and edge surfaces. Pronounced differences in the transient reflection spectroscopies reveal the inconsistent photocarrier and phonon dynamics behaviors on the two surfaces: the slow hot carrier relaxation process is accelerated and the thermoelasticity-induced longitudinal coherent acoustic phonon oscillation completely vanishes on the edge surface, as compared with the basal surface. Theoretical analysis reveals that the inconsistent hot carrier dynamics originate from the anisotropic properties of low-energy phonons in PdSe2, and the absence of phonon oscillation on the edge surface results from the wavevector-limited sensitivity of acoustic B1u mode. Moreover, polarization-dependent spectroscopies indicate the diverse optical anisotropies beyond the in-plane of PdSe2. This work provides a new method to explore unique physical properties and modulate the optical anisotropy of layered materials. [ABSTRACT FROM AUTHOR]

Femtosecond laser direct writing provides an efficient approach to fabricating single nitrogen vacancy (NV) color centers with a relatively high yield. Different from previously reported NV color centers with a random distribution in a bulk diamond or nanocrystals, this gives an opportunity to study the photophysical properties of single NV color centers with precise numbers and positions. However, ultrafast studies on single NV color centers prepared by localization femtosecond laser direct writing are still rare, especially for the graphitization inside a diamond and its relationship with single NV color centers. Here, we report the broadband transient absorption (TA) spectroscopic features of the graphitization and NV color centers in a diamond fabricated by localization femtosecond laser direct writing at room temperature under 400 nm excitation. In comparison with the graphene oxide film, the bleaching features of the graphitization point array in a diamond are similar to reduced graphene oxide, accompanied by excited state absorption signals from local carbon atom vacancy defects in graphene-like structures induced by laser writing. On the other hand, transient features of laser processing array containing single NV color centers with a yield of ∼50% are different from those of the graphitization point array. Our findings suggest that for ultrashort pulse processing of diamonds, broadband TA spectral signals are sensitive to the surrounding atomic environment of processing sites, which could be applied to laser writing point defects in other materials used as solid-state single photon sources. [ABSTRACT FROM AUTHOR]

Integrating aggregation‐induced emission (AIE) into thermally activated delayed fluorescence (TADF) emitters holds great promise for the advancement of highly efficient organic light emitting diodes (OLEDs). Despite recent advancements, a thorough comprehension of the underlying mechanisms remains imperative for the practical application of such materials. In this work, we introduce a novel approach aimed at modulating the TADF process by manipulating dynamic processes in excited states through aggregation effect. Our findings reveal that aggregation not only enhances both prompt and delayed fluorescence simultaneously but also imposes constraints on molecular reorientation. This constraint reinforces spin‐orbit coupling and reduces the energy gap between singlets and triplets. These insights deepen our understanding of the fundamental mechanisms governing the aggregation effect on TADF materials and provide valuable guidance for the design of high‐efficiency photoluminescent materials. [ABSTRACT FROM AUTHOR]

Dynamic protein structures are crucial for deciphering their diverse biological functions. Two-dimensional infrared (2DIR) spectroscopy stands as an ideal tool for tracing rapid conformational evolutions in proteins. However, linking spectral characteristics to dynamic structures poses a formidable challenge. Here, we present a pretrained machine learning model based on 2DIR spectra analysis. This model has learned signal features from approximately 204,300 spectra to establish a "spectrum-structure" correlation, thereby tracing the dynamic conformations of proteins. It excels in accurately predicting the dynamic content changes of various secondary structures and demonstrates universal transferability on real folding trajectories spanning timescales from microseconds to milliseconds. Beyond exceptional predictive performance, the model offers attention-based spectral explanations of dynamic conformational changes. Our 2DIR-based pretrained model is anticipated to provide unique insights into the dynamic structural information of proteins in their native environments. [ABSTRACT FROM AUTHOR]

As excellent functional materials, the composite materials based on graphene and its derivatives (GNDs) have lots of important application values in the emerging fields such as solar energy conversion, and the exploration of electron (or energy) transfer properties of those composites is the key for revealing their further applications. In this review, femtosecond transient absorption spectroscopy (TAS) has been introduced as an essential technique to understand the carrier behaviors in GNDs composites, as well as the advancements of TAS. The specific examples of electron transport in various composite materials characterized by TAS are summarized and discussed, which consist of GNDs with semiconductor quantum dots (QDs), organic dyes, organic polymers, perovskites and other materials, respectively. This review provides a deep insight into the electron transfer (ET) kinetics of various GNDs composites from the perspective of TAS. [ABSTRACT FROM AUTHOR]

In semiconductor‐based microlasers, the generated excited carriers can affect both the optical absorption coefficient and refractive index, influencing the lasing behavior and device performance. In this study, the lasing behavior of individual MAPbBr3 microrods pumped by femtosecond laser pulses is investigated using an ultrafast optical Kerr gating technique. By analyzing the spectral and temporal evolution of the lasing behavior, it is found that the band‐filling (BF) effect can cause a significant change in the refractive index of the material, which results in an unfavorable red‐shift and broadening of the resonant modes, deteriorating the laser linewidth and quality factor. The hot carrier cooling process can provide a buffer for alteration of the energy level occupation state, resulting in a small transient refractive index change and slight red‐shift. These results offer insights into the lasing behavior driven by photogenerated carrier dynamics and provide an optimization strategy for semiconductor‐based microlasers. [ABSTRACT FROM AUTHOR]

4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY)-based molecules have emerged as interesting materials for optoelectronic applications due to the possibility to easily fine-tune their photophysical and optical properties, dominated by two main absorption bands in the visible range. However, no studies have been reported on the nature of these spectral features. By means of ultrafast spectroscopy, we detect intramolecular energy transfer in a spin-coated film of di-thieno-phenyl BODIPY (DTPBDP) dispersed in a polystyrene matrix after pumping the high-energy absorption band. The same effect is not present upon pumping the lowest-energy band, which instead allows the achievement of efficient amplified spontaneous emission. Density functional calculations indicate the different nature of the two main absorption bands, explaining their different photophysical behavior. [ABSTRACT FROM AUTHOR]

Near-infrared two-photon absorption and excited state dynamics of a fluorescent diarylethene (fDAE) derivative were investigated by time-resolved absorption and fluorescence spectroscopies. Prescreening with quantum chemical calculation predicted that a derivative with methylthienyl groups (mt-fDAE) in the closed-ring isomer has a two-photon absorption cross-section larger than 1000 GM, which was experimentally verified by Z-scan measurements and excitation power dependence in transient absorption. Comparison of transient absorption spectra under one-photon and simultaneous two-photon excitation conditions revealed that the closed-ring isomer of mt-fDAE populated into higher excited states deactivates following three pathways on a timescale of ca. 200 fs: (i) the cycloreversion reaction more efficient than that by the one-photon process, (ii) internal conversion into the S1 state, and (iii) relaxation into a lower state (S1' state) different from the S1 state. Time-resolved fluorescence measurements demonstrated that this S1' state is relaxed to the S1 state with the large emission probability. These findings obtained in the present work contribute to extension of the ON–OFF switching capability of fDAE to the biological window and application to super-resolution fluorescence imaging in a two-photon manner. [ABSTRACT FROM AUTHOR]

It is widely believed that the relaxation-induced bleaching signals at nanoseconds observed in ultrafast infrared spectroscopic measurements are due to the local heat effect resulting from the thermalization of the infrared excitations. In this work, combining ultrafast IR pump/probe, 2D-IR, visible pump/IR probe, and ultrafast visible/IR double resonant fluorescence experiments, the vibrational hot ground states of fluorescein dianion in methanol solutions are found to be unexpectedly long, at the time scale of nanoseconds. This result indicates that the long-standing bleaching signal observed in the nonlinear IR experiments must have significant contributions from these hot ground states for the initial couple of ns. It is likely that a similar mechanism can also hold for other molecular systems. The hot ground states can last much longer than conventionally expected, which can potentially be applied to modify chemical reactions. [ABSTRACT FROM AUTHOR]

The size tunable color of colloidal semiconductor quantum dots (QDs) is probably the most elegant illustration of the quantum confinement effect. As explained by the simple "particle‐in‐a‐box" model, the transition energies between the levels increase when the "box" becomes smaller. To investigate quantum confinement effects, typically a well‐defined narrow size distribution of the nanoparticles is needed. In this contribution, how coherent electronic two‐dimensional spectroscopy (2DES) can directly visualize the quantum size effect in a sample with broad size distribution of QDs is demonstrated. The method is based on two features of the 2DES – the ability to resolve inhomogeneous broadening and the capability to reveal correlations between the states. In QD samples, inhomogeneous spectral broadening is mainly caused by the size distribution and leads to elongated diagonal peaks of the spectra. Since the cross peaks correlate the energies of two states, they allow drawing conclusions about the size dependence of the corresponding states. It is also found that the biexciton binding energy changes between 3 and 8 meV with the QD size. Remarkably, the size dependence is non‐monotonic with a clear minimum. [ABSTRACT FROM AUTHOR]

Cyanobacteria respond to iron limitation by producing the pigment-protein complex IsiA, forming rings associated with photosystem I (PSI). Initially considered a chlorophyll-storage protein, IsiA is known to act as an auxiliary light-harvesting antenna of PSI, increasing its absorption cross-section and reducing the need for iron-rich PSI core complexes. Spectroscopic studies have demonstrated efficient energy transfer from IsiA to PSI. Here we investigate the room-temperature excitation dynamics in isolated PSI-IsiA, PSI, IsiA monomer complexes and IsiA aggregates using two-dimensional electronic spectroscopy. Cross analyses of the data from these three samples allow us to resolve components of energy transfer between IsiA and PSI with lifetimes of 2--3 ps and around 20 ps. Structure-based Förster theory calculations predict a single major timescale of IsiA-PSI equilibration, that depends on multiple energy transfer routes between different IsiA subunits in the ring. Despite the experimentally observed lifetime heterogeneity, which is attributed to structural heterogeneity of the supercomplexes, IsiA is found to be a unique, highly efficient, membrane antenna complex in cyanobacteria. [ABSTRACT FROM AUTHOR]

In fatty acid photodecarboxylase (FAP), light‐induced formation of the primary radical product RCOO⋅ from fatty acid RCOO− occurs in 300 ps, upon which CO2 is released quasi‐immediately. Based on the hypothesis that aliphatic RCOO⋅ (spectroscopically uncharacterized because unstable) absorbs in the red similarly to aromatic carbonyloxy radicals such as 2,6‐dichlorobenzoyloxy radical (DCB⋅), much longer‐lived linear RCOO⋅ has been suggested recently. We performed quantum chemical reaction pathway and spectral calculations. These calculations are in line with the experimental DCB⋅ decarboxylation dynamics and spectral properties and show that in contrast to DCB⋅, aliphatic RCOO⋅ radicals a) decarboxylate with a very low energetic barrier and on the timescale of a few ps and b) exhibit little red absorption. A time‐resolved infrared spectroscopy experiment confirms very rapid, ≪300 ps RCOO⋅ decarboxylation in FAP. We argue that this property is required for the observed high quantum yield of hydrocarbons formation by FAP. [ABSTRACT FROM AUTHOR]

Organic‐inorganic heterostructures play a pivotal role in modern electronic and optoelectronic applications including photodetectors and field effect transistors, as well as in solar energy conversion such as photoelectrodes of dye‐sensitized solar cells, photoelectrochemical cells, and in organic photovoltaics. To a large extent, performance of such devices is controlled by charge transfer dynamics at and across (inner) interfaces, e.g. between a wide band gap semiconductor and molecular sensitizers and/or catalysts. Hence, a detailed understanding of the structure‐dynamics‐function relationship of such functional interfaces is necessary to rationalize possible performance limitations of these materials and devices on a molecular level. Vibrational sum‐frequency generation (VSFG) spectroscopy, as an interface‐sensitive spectroscopic technique, allows to obtain chemically specific information from interfaces and combines such chemical insights with ultrafast time resolution, when integrated as a spectroscopic probe into a pump‐probe scheme. Thus, this minireview discusses the advantages and potential of VSFG spectroscopy for investigating interfacial charge transfer dynamics and structural changes at inner interfaces. A critical perspective of the unique spectroscopic view of otherwise inaccessible interfaces is presented, which we hope opens new opportunities for an improved understanding of function‐determining processes in complex materials, and brings together communities who are devoted to designing materials and devices with spectroscopists. [ABSTRACT FROM AUTHOR]

Photosystem I (PS I) is a photosynthetic pigment–protein complex that absorbs light and uses the absorbed energy to initiate electron transfer. Electron transfer has been shown to occur concurrently along two (A- and B-) branches of reaction center (RC) cofactors. The electron transfer chain originates from a special pair of chlorophyll a molecules (P700), followed by two chlorophylls and one phylloquinone in each branch (denoted as A−1, A0, A1, respectively), converging in a single iron–sulfur complex Fx. While there is a consensus that the ultimate electron donor–acceptor pair is P700+A0−, the involvement of A−1 in electron transfer, as well as the mechanism of the very first step in the charge separation sequence, has been under debate. To resolve this question, multiple groups have targeted electron transfer cofactors by site-directed mutations. In this work, the peripheral hydrogen bonds to keto groups of A0 chlorophylls have been disrupted by mutagenesis. Four mutants were generated: PsaA-Y692F; PsaB-Y667F; PsaB-Y667A; and a double mutant PsaA-Y692F/PsaB-Y667F. Contrary to expectations, but in agreement with density functional theory modeling, the removal of the hydrogen bond by Tyr → Phe substitution was found to have a negligible effect on redox potentials and optical absorption spectra of respective chlorophylls. In contrast, Tyr → Ala substitution was shown to have a fatal effect on the PS I function. It is thus inferred that PsaA-Y692 and PsaB-Y667 residues have primarily structural significance, and their ability to coordinate respective chlorophylls in electron transfer via hydrogen bond plays a minor role. [ABSTRACT FROM AUTHOR]

In the realm of optoelectronic applications, the incorporation of a metal interlayer between layers of a topological material holds significant potential. The interlayer introduces benefits such as improved charge transfer efficiency, tunable band alignment, plasmonics effect, and enhanced light‐matter interactions, paving the way for more efficient and versatile optoelectronic devices. This work explores the incorporation of gold between Bi2Se3, resulting in an enhancement in the response time of photoresponse of interlayered systems (Bi2Se3‐Au‐Bi2Se3). The introduction of a gold interlayer between Bi2Se3 significantly influences the overlayer structure, crystallinity, crystallite size, and even phonon behavior. Moreover, the responsivity of the interlayered device at a bias (2 V) is found to have high responsivity with fast response and decay time (τr = 0.1 ms, and τd = 24 ms of interlayered systems) as compared to intrinsic Bi2Se3(τr = 0.6 ms, and τd = 28 ms). This change is attributed to the bandgap alteration of the Bi2Se3/Au interface, which is monitored through transient spectroscopy performed at different electric biases. This study suggests that incorporating a gold interlayer holds potential benefits for various optoelectronic applications. [ABSTRACT FROM AUTHOR]

In the realm of optoelectronic applications, the incorporation of a metal interlayer between layers of a topological material holds significant potential. The interlayer introduces benefits such as improved charge transfer efficiency, tunable band alignment, plasmonics effect, and enhanced light‐matter interactions, paving the way for more efficient and versatile optoelectronic devices. This work explores the incorporation of gold between Bi2Se3, resulting in an enhancement in the response time of photoresponse of interlayered systems (Bi2Se3‐Au‐Bi2Se3). The introduction of a gold interlayer between Bi2Se3 significantly influences the overlayer structure, crystallinity, crystallite size, and even phonon behavior. Moreover, the responsivity of the interlayered device at a bias (2 V) is found to have high responsivity with fast response and decay time (τr = 0.1 ms, and τd = 24 ms of interlayered systems) as compared to intrinsic Bi2Se3(τr = 0.6 ms, and τd = 28 ms). This change is attributed to the bandgap alteration of the Bi2Se3/Au interface, which is monitored through transient spectroscopy performed at different electric biases. This study suggests that incorporating a gold interlayer holds potential benefits for various optoelectronic applications. [ABSTRACT FROM AUTHOR]

We present mass‐correlated rotational alignment spectroscopy and the first high‐resolution rotational Raman spectra for furan. Spectra were measured with a spectral range up to 0.5 THz and a resolution down to 1.6 MHz. Spectra for 13C and 18O isotopologues were observed in their corresponding mass channels at natural abundance. Based on our data and literature constants, we performed a purely experimental structure analysis for the effective and equilibrium structures of furan. The results highlight the utility of CRASY to obtain rare isotopologue spectra without isotopically enriched samples. [ABSTRACT FROM AUTHOR]

Epitaxial perovskite heterostructures consisting noble metal nanoparticles have been received immense interest in hot carrier photovoltaic devices and photocatalysis. The major understanding of carrier extraction across the interface of perovskite heterostructure have shown exciting interest for next generation device applications. In the present study, dodecahedron CsPbBr3/Au heterostructure was synthesized via hot injection method. From HR‐TEM images, we observed direct epitaxial growth between (110) plane of CsPbBr3 and (111) plane of Au nanoparticle (NPs), which was further supported by steady‐state and time‐resolved photoluminescence studies. Further, femtosecond transient absorption spectroscopy has been utilized to understand the charge transfer dynamics of synthesized samples. In CsPbBr3/Au heterostructure, faster recovery has been noticed than that of pristine CsPbBr3, which clearly suggests transfer of electrons from the conduction band of CsPbBr3 to Au NPs. The distinct fast electron transfer in the CsPbBr3/Au heterostructure can be mainly ascribed to the epitaxial growth and strong electronic coupling between CsPbBr3 and Au NPs. The reduced bleach intensity, faster bleach growth and recovery kinetics strongly suggest efficient electron transfer from CsPbBr3 NCs to Au NPs. These findings clearly establish that architecture of metal and perovskite heterostructures may pave way to develop suitable alternative for highly efficient photovoltaic devices and photocatalysis applications. [ABSTRACT FROM AUTHOR]

We establish a general kinetic scheme for the energy transfer and radical-pair dynamics in photosystem I (PSI) of Chlamydomonas reinhardtii, Synechocystis PCC6803, Thermosynechococcus elongatus and Spirulina platensis grown under white-light conditions. With the help of simultaneous target analysis of transient-absorption data sets measured with two selective excitations, we resolved the spectral and kinetic properties of the different species present in PSI. WL-PSI can be described as a Bulk Chl a in equilibrium with a higher-energy Chl a, one or two Red Chl a and a reaction-center compartment (WL-RC). Three radical pairs (RPs) have been resolved with very similar properties in the four model organisms. The charge separation is virtually irreversible with a rate of ≈900 ns−1. The second rate, of RP1 → RP2, ranges from 70–90 ns−1 and the third rate, of RP2 → RP3, is ≈30 ns−1. Since RP1 and the Red Chl a are simultaneously present, resolving the RP1 properties is challenging. In Chlamydomonas reinhardtii, the excited WL-RC and Bulk Chl a compartments equilibrate with a lifetime of ≈0.28 ps, whereas the Red and the Bulk Chl a compartments equilibrate with a lifetime of ≈2.65 ps. We present a description of the thermodynamic properties of the model organisms at room temperature. [ABSTRACT FROM AUTHOR]

Cumulenes are linear molecules consisting of consecutive double bonds linking chains of sp-hybridized carbon atoms. They have primarily been of interest for potential use as molecular wires or in other nanoscale electronic devices, but more recently, other applications such as catalysis or even light harvesting through singlet fission have been speculated. Despite the recent theoretical and experimental interest, the photoexcitation of cumulenes typically results in quenching on the picosecond timescale, and the exact quenching mechanism for even the simplest of [3]-cumulenes lacks a clear explanation. In this report, we perform transient absorption spectroscopy on a set of model [3]-cumulene derivatives in a wide range of environmental conditions to demonstrate that the planarization of phenyl groups ultimately quenches the excited state. By restricting this intramolecular motion, we increase the excited state lifetime by a few nanoseconds, strongly enhancing photoluminescence and demonstrating an approach to stabilize them for photochemical applications.

Two-dimensional (2D) layered materials exhibit strong light-matter interactions, remarkable excitonic effects, and ultrafast optical response, making them promising for high-speed on-chip nanophotonics. Recently, significant attention has been directed towards anisotropic 2D materials (A2DMs) with low in-plane crystal symmetry. These materials present unique optical properties dependent on polarization and direction, offering additional degrees of freedom absent in conventional isotropic 2D materials. In this review, we discuss recent progress in understanding the fundamental aspects and ultrafast nanophotonic applications of A2DMs. We cover structural characteristics and anisotropic linear/nonlinear optical properties of A2DMs, including well-studied black phosphorus and rhenium dichalcogenides, as well as emerging quasi-one-dimensional materials. Then, we discuss fundamental ultrafast anisotropic phenomena occurring in A2DMs, such as polarization-dependent ultrafast dynamics of charge carriers and excitons, their direction-dependent spatiotemporal diffusion, photo-induced symmetry switching, and anisotropic coherent acoustic phonons. Furthermore, we review state-of-the-art ultrafast nanophotonic applications based on A2DMs, including polarization-driven active all-optical modulations and ultrafast pulse generations. This review concludes by offering perspectives on the challenges and future prospects of A2DMs in ultrafast nanophotonics.

The photosystem II core complex (PSII-CC) is the smallest subunit of the oxygenic photosynthetic apparatus that contains core antennas and a reaction center, which together allow for rapid energy transfer and charge separation, ultimately leading to efficient solar energy conversion. However, there is a lack of consensus on the interplay between the energy transfer and charge separation dynamics of the core complex. Here, we report the application of two-dimensional electronic-vibrational (2DEV) spectroscopy to the spinach PSII-CC at 77 K. The simultaneous temporal and spectral resolution afforded by 2DEV spectroscopy facilitates the separation and direct assignment of coexisting dynamical processes. Our results show that the dominant dynamics of the PSII-CC are distinct in different excitation energy regions. By separating the excitation regions, we are able to distinguish the intraprotein dynamics and interprotein energy transfer. Additionally, with the improved resolution, we are able to identify the key pigments involved in the pathways, allowing for a direct connection between dynamical and structural information. Specifically, we show that C505 in CP43 and the peripheral chlorophyll ChlzD1 in the reaction center are most likely responsible for energy transfer from CP43 to the reaction center.

Colloidal semiconductor nanoplatelets (NPLs) have emerged as low‐cost and free‐standing alternates of traditional quantum wells. The giant heavy‐ and light‐hole splitting in NPLs allows for efficient optical spin injection. However, the electron spin lifetimes for prototypical CdSe NPLs are within a few picoseconds, likely limited by strong electron‐hole exchange in these quantum‐ and dielectric‐confined materials. Here how this hurdle can be overcome with engineered NPL‐heterostructures is demonstrated. By constructing type‐I CdSe/ZnS core/shell NPLs, dielectric screening inside the core is strongly enhanced, prolonging the electron spin polarization time (τesp) to over 30 ps (or 60 ps electron spin‐flip time). Alternatively, by growing type‐II CdSe/CdTe core/crown NPLs to spatially separate electron and hole wavefunctions, the electron‐hole exchange is strongly suppressed, resulting in τesp as long as 300 ps at room temperature. This study not only exemplifies how the well‐established synthetic chemistry of colloidal heterostructures can aid in spin dynamics control but also establishes the feasibility of room‐temperature coherent spin manipulation in colloidal NPLs. [ABSTRACT FROM AUTHOR]

Compounds with multiple photoswitching units are appealing for complex photochemical control of molecular materials and nanostructures. Herein, we synthesized novel meta‐ and para‐ connected (related to the nitrogen of the indoline) azobenzene‐spiropyran dyads, in which the central benzene unit is shared by both switches. We investigated their photochemistry using static and time‐resolved transient absorption spectroscopy as well as quantum chemical calculations. In the meta‐compound, the individual components are photochemically decoupled due to the meta‐pattern. In the para‐compound the spiro‐connectivity leads to a bifunctional photoswitchable system with a red‐shifted absorption. The azobenzene and the spiropyran can thus be addressed and switched independently by light of appropriate wavelength. Through the different connectivity patterns two different orthogonally photoswitchable systems have been obtained which are promising candidates for complex applications of light control. [ABSTRACT FROM AUTHOR]

Cumulenes are linear molecules consisting of consecutive double bonds linking chains of sp-hybridized carbon atoms. They have primarily been of interest for potential use as molecular wires or in other nanoscale electronic devices, but more recently, other applications such as catalysis or even light harvesting through singlet fission have been speculated. Despite the recent theoretical and experimental interest, the photoexcitation of cumulenes typically results in quenching on the picosecond timescale, and the exact quenching mechanism for even the simplest of [3]-cumulenes lacks a clear explanation. In this report, we perform transient absorption spectroscopy on a set of model [3]-cumulene derivatives in a wide range of environmental conditions to demonstrate that the planarization of phenyl groups ultimately quenches the excited state. By restricting this intramolecular motion, we increase the excited state lifetime by a few nanoseconds, strongly enhancing photoluminescence and demonstrating an approach to stabilize them for photochemical applications. [ABSTRACT FROM AUTHOR]

Triplet dynamics in singlet fission depend strongly on the strength of the electronic coupling. Covalent systems in solution offer precise control over such couplings. Nonetheless, efficient free triplet generation remains elusive in most systems, as the intermediate triplet pair 1(T1T1) is prone to triplet‐triplet annihilation due to its spatial confinement. In the solid state, entropically driven triplet diffusion assists in the spatial separation of triplets, resulting in higher yields of free triplets. Control over electronic coupling in the solid state is, however, challenging given its sensitivity to molecular packing. We have thus developed a hexameric system (HexPnc) to enable solid‐state‐like triplet diffusion at the molecular scale. This system is realized by covalently tethering three pentacene dimers to a central subphthalocyanine scaffold. Transient absorption spectroscopy, complemented by theoretical structural optimizations and steady‐state spectroscopy, reveals that triplet diffusion is indeed facilitated due to intramolecular cluster formation. The yield of free triplets in HexPnc is increased by a factor of up to 14 compared to the corresponding dimeric reference (DiPnc). Thus, HexPnc establishes crucial design aspects for achieving efficient triplet dissociation in strongly coupled systems by providing avenues for diffusive separation of 1(T1T1), while, concomitantly, retaining strong interchromophore coupling which preserves rapid formation of 1(T1T1). [ABSTRACT FROM AUTHOR]

The heavy‐metal‐free ZnSeTe quantum dots (QDs) hold great promise for the development of modern optoelectronic devices, yet, the nature of the emissive state within remains elusive. Herein, the different emission origins are clarified for the ZnSeTe QDs with dilute and heavy Te contents based on multiple spectroscopic characterizations and first‐principles calculation. In the case of dilute Te incorporation (Te/Se < 20%), the low‐energy tail of the asymmetric emission is ascribed to the recombination from the localized state induced by Te clusters, and the the hot carrier localization process occurs within a timescale of ≈500 fs. As the Te/Se ratio increases above 20%, the charge density difference shows a uniform distribution due to the decrease in electronegativity contrast, such that the carriers become delocalized and tail emission disappears. Meanwhile, the emission line‐width broadens mainly originating from the inhomogeneous broadening effect. These findings are constructive for developing sustainable QDs toward optoelectronic applications. [ABSTRACT FROM AUTHOR]

Benefiting from the synergistic development of material design, device engineering, and the mechanistic understanding of device physics, the certified power conversion efficiencies (PCEs) of single‐junction non‐fullerene organic solar cells (OSCs) have already reached a very high value of exceeding 19%. However, in addition to PCEs, the poor stability is now a challenging obstacle for commercial applications of organic photovoltaics (OPVs). Herein, recent progress made in exploring operational mechanisms, anomalous photoelectric behaviors, and improving long‐term stability in non‐fullerene OSCs are highlighted from a novel and previously largely undiscussed perspective of engineering exciton and charge carrier pathways. Considering the intrinsic connection among multiple temporal‐scale photocarrier dynamics, multi‐length scale morphologies, and photovoltaic performance in OPVs, this review delineates and establishes a comprehensive and in‐depth property‐function relationship for evaluating the actual device stability. Moreover, this review has also provided some valuable photophysical insights into employing the advanced characterization techniques such as transient absorption spectroscopy and time‐resolved fluorescence imagings. Finally, some of the remaining major challenges related to this topic are proposed toward the further advances of enhancing long‐term operational stability in non‐fullerene OSCs. [ABSTRACT FROM AUTHOR]

Electron–phonon coupling (EPC) and phonon–phonon scattering (PPS) are at the core of the microscopic physics mechanisms of vast quantum materials. However, to date, there are rarely reports that these two processes can be spatially separated, although they are usually temporally detached with different characteristic lifetimes. Here, by employing ultrafast spectroscopy to investigate the photo‐carrier ultrafast dynamics in a LaCoO3 thin film on a (100) SrTiO3 substrate, intriguing evidence is found that the two interactions are indeed spatially separated. The EPC mainly occurs in the thin film, whereas PPS is largely in the substrate, especially at the several atomic layers near the interface. Across‐interface penetration and decay of optical phonons into acoustic phonons thus naturally occur. An EPC strength λEg = 0.30 is also obtained and an acoustic phonon mode at 45.3 GHz is observed. The finding lays out a cornerstone for future quantum nano device designs. [ABSTRACT FROM AUTHOR]

Electron–phonon coupling (EPC) and phonon–phonon scattering (PPS) are at the core of the microscopic physics mechanisms of vast quantum materials. However, to date, there are rarely reports that these two processes can be spatially separated, although they are usually temporally detached with different characteristic lifetimes. Here, by employing ultrafast spectroscopy to investigate the photo‐carrier ultrafast dynamics in a LaCoO3 thin film on a (100) SrTiO3 substrate, intriguing evidence is found that the two interactions are indeed spatially separated. The EPC mainly occurs in the thin film, whereas PPS is largely in the substrate, especially at the several atomic layers near the interface. Across‐interface penetration and decay of optical phonons into acoustic phonons thus naturally occur. An EPC strength λEg = 0.30 is also obtained and an acoustic phonon mode at 45.3 GHz is observed. The finding lays out a cornerstone for future quantum nano device designs. [ABSTRACT FROM AUTHOR]

Phenol blue (PhB) is a dye that exhibits positive solvatochromism which is also nonfluorescent due to its ultrashort excited state lifetime. We have conducted femtosecond time‐resolved transient absorption (TA) spectroscopic measurements of a PhB solution using two distinct excitation wavelengths, at shorter and longer wavelength sides of the visible absorption band. The results revealed that a long‐lived heterogeneity exists in protic solvents whereas, in aprotic solvents, the system rapidly returns to the original thermal equilibrium on the ultrafast timescale. Interestingly, the lifetime of the heterogeneity is longer for methanol (MeOH) compared to ethanol (EtOH) solution suggesting stronger interaction between PhB and MeOH. Additionally, since the excited state lifetime of PhB was still in the sub‐picosecond domain even in a polymer matrix, we suggest a nonradiative decay mechanism through high‐frequency vibrational modes without involving large structural reconfiguration such as twisting of the benzoquinone (BzQ) moiety. [ABSTRACT FROM AUTHOR]

Dynamic topological photonics is a novel research field, combining the time-domain optics and topological physics. In this review, the recent progress and realization platforms of dynamic topological photonics have been well introduced. The definition, measurement methods and the evolution process of the dynamic topological photonics are demonstrated to better understand the physical diagram. This review is meant to bring the readers a different perspective on topological photonics, grasp the advanced progress of dynamic topology, and inspire ideas about future prospects. [ABSTRACT FROM AUTHOR]

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 0.71 ps and 3.28 ps at 140 K (0.17 and 1.33 ps at 296 K), respectively and that the pheophytin anion (PheoD1−) is generated with the time-constant of 43.0 ps at 140 K (14.8 ps at 296 K) upon excitation into the Qy band of chlorophyll a at 670 nm. The secondary electron transfer to quinone QA: PheoD1−QA → PheoD1QA− is observed with the time-constant of 650 ps only at 296 K. On the other hand, an inefficient β-carotene → chlorophyll a energy transfer (33%) occurred after excitation to the S2 state of β-carotene at 500 nm. Instead, the carotenoid triplet state appeared in an ultrafast timescale after excitation at 500 nm. [ABSTRACT FROM AUTHOR]

As one of the emerging two-dimensional lead halide materials, lead iodide (PbI2) nanosheets have proven to possess strong application potential in the fields of high-energy radiation detection and highly efficient perovskite solar cells. However, the underlying photophysical properties such as hot-exciton-related carrier dynamics remain unclear for PbI2 nanosheets. Here, we report the exciton dynamics of a single PbI2 nanoflake prepared by an aqueous solution method. Through a three-dimensional (3D) diffusion model, we obtain the exciton annihilation radius and diffusion coefficient of a single PbI2 nanoflake under non-resonant and resonant excitation conditions of band-edge exciton state. As initial exciton densities increase, we find the carrier recombination mechanism for a single PbI2 nanoflake gradually changes from exciton-exciton annihilation to free-carrier recombination. Finally, we reveal the room-temperature circular polarization of a single PbI2 nanoflake is due to free-carrier recombination with a band-edge exciton dissociation time of ~120 fs under the resonant excitation condition. [ABSTRACT FROM AUTHOR]

Cyanobacteria respond to iron limitation by producing the pigment-protein complex IsiA, forming rings associated with photosystem I (PSI). Initially considered a chlorophyll-storage protein, IsiA is known to act as an auxiliary light-harvesting antenna of PSI, increasing its absorption cross-section and reducing the need for iron-rich PSI core complexes. Spectroscopic studies have demonstrated efficient energy transfer from IsiA to PSI. Here we investigate the room-temperature excitation dynamics in isolated PSI–IsiA, PSI, IsiA monomer complexes and IsiA aggregates using two-dimensional electronic spectroscopy. Cross analyses of the data from these three samples allow us to resolve components of energy transfer between IsiA and PSI with lifetimes of 2—3 ps and around 20 ps. Structure-based Förster theory calculations predict a single major timescale of IsiA-PSI equilibration, that depends on multiple energy transfer routes between different IsiA subunits in the ring. Despite the experimentally observed lifetime heterogeneity, which is attributed to structural heterogeneity of the supercomplexes, IsiA is found to be a unique, highly efficient, membrane antenna complex in cyanobacteria.

Artificial photocatalytic energy conversion is a very interesting strategy to solve energy crises and environmental problems by directly collecting solar energy, but low photocatalytic conversion efficiency is a bottleneck that restricts the practical application of photocatalytic reactions. The key issue is that the photo-generated charge separation process spans a huge spatio-temporal scale from femtoseconds to seconds, and involves complex physical processes from microscopic atoms to macroscopic materials. Femtosecond transient absorption (fs-TA) spectroscopy is a powerful tool for studying electron transfer paths in photogenerated carrier dynamics of photocatalysts. By extracting the attenuation characteristics of the spectra, the quenching path and lifetimes of carriers can be simulated on femtosecond and picosecond time scales. This paper introduces the principle of transient absorption, typical dynamic processes and the application of femtosecond transient absorption spectroscopy in photocatalysis, and summarizes the bottlenecks faced by ultrafast spectroscopy in photocatalytic applications, as well as future research directions and solutions. This will provide inspiration for understanding the charge transfer mechanism of photocatalytic processes.

Protein secondary structure discrimination is crucial for understanding their biological function. It is not generally possible to invert spectroscopic data to yield the structure. We present a machine learning protocol which uses two-dimensional UV (2DUV) spectra as pattern recognition descriptors, aiming at automated protein secondary structure determination from spectroscopic features. Accurate secondary structure recognition is obtained for homologous (97%) and nonhomologous (91%) protein segments, randomly selected from simulated model datasets. The advantage of 2DUV descriptors over one-dimensional linear absorption and circular dichroism spectra lies in the cross-peak information that reflects interactions between local regions of the protein. Thanks to their ultrafast (∼200 fs) nature, 2DUV measurements can be used in the future to probe conformational variations in the course of protein dynamics.

Photochromic fluorescent proteins (FPs) have proved to be indispensable luminous probes for sophisticated and advanced bioimaging techniques. Among them, an interplay between photoswitching and photoconversion has only been observed in a limited subset of Kaede-like FPs that show potential for discovering the key mechanistic steps during green-to-red photoconversion. Various spectroscopic techniques including femtosecond stimulated Raman spectroscopy (FSRS), X-ray crystallography, and femtosecond transient absorption were employed on a set of five related FPs with varying photoconversion and photoswitching efficiencies. A 3-methyl-histidine chromophore derivative, incorporated through amber suppression using orthogonal aminoacyl tRNA synthetase/tRNA pairs, displays more dynamic photoswitching but greatly reduced photoconversion versus the least-evolved ancestor (LEA). Excitation-dependent measurements of the green anionic chromophore reveal that the varying photoswitching efficiencies arise from both the initial transient dynamics of the bright cis state and the final trans-like photoswitched off state, with an exocyclic bridge H-rocking motion playing an active role during the excited-state energy dissipation. This investigation establishes a close-knit feedback loop between spectroscopic characterization and protein engineering, which may be especially beneficial to develop more versatile FPs with targeted mutations and enhanced functionalities, such as photoconvertible FPs that also feature photoswitching properties. [ABSTRACT FROM AUTHOR]

Single‐crystal halide perovskites are among the most promising semiconductor candidates for highly efficient optoelectronic devices due to their higher stability against moisture and light radiation and lower trap density than their polycrystalline counterparts. In this work, single‐crystal MAPbBr3 microcavities with controllable geometries and sizes are fabricated using a template‐limited method combined with an anti‐solvent diffusion growth method. The single‐crystal microcavities emit lasers around 550 nm under femtosecond laser excitation, with a lasing threshold of ≈35 µJ cm−2 and a quality factor of 1135, as well as excellent long‐term operation stability. The temporal‐spatial evolution of the lasing process in an individual microcavity is achieved by the microscopic optical Kerr‐gating technique. The temporal behaviors including pulse duration and build‐up time, emission spectra shift, and lasing mode evolution as a function of pump fluence are unveiled, and the complex relationship between the light‐induced carrier dynamics and lasing properties is clarified. Spatial heterogeneous lasing dynamics are also observed in an individual microdisk, which is attributed to the non‐uniform optical losses and carrier densities driven by structural imperfections. This study can provide a fabrication strategy for perovskite on‐chip optoelectronic devices, as well as a deeper understanding of the carrier‐density‐driven lasing dynamics in microcavities. [ABSTRACT FROM AUTHOR]

The optical properties of doped metal nanoclusters (NCs) have stimulated great research interests because of their applications in biosensing and photocatalysis. The photoluminescence and excited state dynamics of MAu24(SR)18 are complicated and the detailed mechanism has not been fully understood. Here, we investigate the exciton and vibrational dynamics of two doped NCs MAu24(SR)18 (M=Pd, Pt; SR stands for phenylethanethiolate) by ultrafast spectroscopy. In contrast to the parent Au25(SR)18 NCs, Pd and Pt doping significantly reduce the exciton lifetime by several orders of magnitude. We find that the ultrashort exciton lifetimes of PtAu24 (5 ps) and PdAu24 (30 ps) are ascribed to the ultrasmall energy gap (Eg=0.3 eV). In both two doped NCs, we observe significant coherent vibrations (2.4 THz) that arise from the metal core, which indicates these oscillations can survive regardless of the short exciton lifetime. Unravelling the effect of foreign atom doping on the exciton and vibrational dynamics of metal NCs will provide new insight into their optical properties and help designing these molecular-like nanostructures for specific applications. [ABSTRACT FROM AUTHOR]

The family of two-dimensional (2D) layered materials with strong excitonic effect offers fascinating opportunities for studying excited state exciton behavior at 2D limit. While exciton dynamics in conventional 2D semiconductors (e.g. transition metal dichalcogenides) has been extensively studied, little is known about exciton properties and dynamics in 2D layered semiconductors with strong electron/exciton-phonon coupling. Here, by combining experimental and theoretical approaches, we reveal the intrinsic highly localized exciton (i.e. self-trapped exciton) in 2D layered As2S3, driven by strong exciton-phonon interaction. It is shown that photoexcited electron/hole charges in As2S3 localize spontaneously in ~110 fs, giving rise to large stokes-shifted and broad photoluminescence. An interlayer partial bond is formed between chalcogen atoms, triggering lattice distortion and carrier localization. Together with Urbach-Martienssen analysis, this study provides a comprehensive physical picture to understand the complex interplay between exciton and lattice dynamics in 2D semiconductors, which has strong implications to their optoelectronic properties and applications. [ABSTRACT FROM AUTHOR]