Acoustic phonon excitation in gold probed by time-resolved photoemission electron microscopy.

Electron-phonon coupling is an important energy transfer mechanism in solids after ultrafast laser excitation. In this study, we present an extreme ultraviolet (EUV) and infrared (IR) pump-probe photoemission experiment to investigate the electron-phonon coupling in nonequilibrium gold. The energy of IR-laser-emitted photoelectrons is shifted due to the EUV photoemission and oscillates with a ∼4THz frequency. Such oscillation is considered as the effective excitation of the longitudinal acoustic phonon mode in gold through the spectral-dependent electron-phonon coupling. Our study showcases the capability of time-resolved photoemission electron microscopy to monitor the non-equilibrium lattice vibrations with ultrahigh spatial and temporal resolution.

Controlling the Polarization of Nitrogen Ion Lasing.

Air lasing provides a promising technique to remotely produce coherent radiation in the atmosphere and has attracted continuous attention. However, the polarization properties of N2+ lasing with seeding have not been understood since it was discovered 10 years ago, in which the polarization behaviors appear disordered and confusing. Here, we performed an experimental and theoretical investigation of the polarization properties of N2+ lasing and successfully revealed its underlying physical mechanism. We found that the optical gain is anisotropic, owing to the permanent alignment of N2+ induced by the preferential ionization of the pump light. As a result, the polarization of the N2+ lasing tends to align with that of the pump light after amplification, which becomes more pronounced as the amplification factor increases. Based on the permanent alignment of N2+, we built a theoretical model that analytically interpreted and numerically reproduced the experimental observations, which points out the key factors for controlling the polarization of N2+ lasing.

Structure and Ultrafast X-ray Diffraction of the Hydrated Metaphosphate.

We study the pathway of metaphosphate hydration when a metaphosphate anion is dissolved in liquid water with an explicit water model. For this purpose, we propose a sequential Monte Carlo algorithm incorporated with the ab initio quantum mechanics/molecular mechanics (QM/MM) method, which can reduce the amount of ab initio QM/MM sampling while retaining the accuracy of the simulation. We demonstrate the numerical calculation of the standard enthalpy change for the successive addition reaction PO3-·2H2O + H2O ⇌ PO3-·3H2O in the liquid phase, which helps to clarify the hydration pathway of the metaphosphate. With the obtained hydrated structure of the metaphosphate anion, we perform ab initio calculations for its relaxation dynamics upon vibrational excitation and characterize the energy transfer process in solution with simulated ultrafast X-ray diffraction signals, which can be experimentally implemented with X-ray free-electron lasers.

Layer-dependent ultrafast carrier dynamics of PdSe2 investigated by photoemission electron microscopy.

For atomically thin two-dimensional materials, variations in layer thickness can result in significant changes in the electronic energy band structure and physicochemical properties, thereby influencing the carrier dynamics and device performance. In this work, we employ time- and energy-resolved photoemission electron microscopy to reveal the ultrafast carrier dynamics of PdSe2 with different layer thicknesses. We find that for few-layer PdSe2 with a semiconductor phase, an ultrafast hot carrier cooling on a timescale of approximately 0.3 ps and an ultrafast defect trapping on a timescale of approximately 1.3 ps are unveiled, followed by a slower decay of approximately tens of picoseconds. However, for bulk PdSe2 with a semimetal phase, only an ultrafast hot carrier cooling and a slower decay of approximately tens of picoseconds are observed, while the contribution of defect trapping is suppressed with the increase of layer number. Theoretical calculations of the electronic energy band structure further confirm the transition from a semiconductor to a semimetal. Our work demonstrates that TR- and ER-PEEM with ultrahigh spatiotemporal resolution and wide-field imaging capability has great advantages in revealing the intricate details of ultrafast carrier dynamics of nanomaterials.

Direct Hot-Electron Transfer at the Au Nanoparticle/Monolayer Transition-Metal Dichalcogenide Interface Observed with Ultrahigh Spatiotemporal Resolution.

Plasmon-induced hot-electron transfer at the metallic nanoparticle/semiconductor interface is the basis of plasmon-enhanced photocatalysis and energy harvesting. However, limited by the nanoscale size of hot spots and femtosecond time scale of hot-electron transfer, direct observation is still challenging. Herein, by using spatiotemporal-resolved photoemission electron microscopy with a two-color pump-probe beamline, we directly observed such a process with a concise system, the Au nanoparticle/monolayer transition-metal dichalcogenide (TMD) interface. The ultrafast hot-electron transfer from Au nanoparticles to monolayer TMDs and the plasmon-enhanced transfer process were directly measured and verified through an in situ comparison with the Au film/TMD interface and free TMDs. The lifetime at the Au nanoparticle/MoSe2 interface decreased from 410 to 42 fs, while the photoemission intensities exhibited a 27-fold increase compared to free MoSe2. We also measured the evolution of hot electrons in the energy distributions, indicating the hot-electron injection and decay happened in an ultrafast time scale of ∼50 fs without observable electron cooling.

Spatiotemporal imaging and shaping of electron wave functions using novel attoclock interferometry.

Electrons detached from atoms by photoionization carry valuable information about light-atom interactions. Characterizing and shaping the electron wave function on its natural timescale is of paramount importance for understanding and controlling ultrafast electron dynamics in atoms, molecules and condensed matter. Here we propose a novel attoclock interferometry to shape and image the electron wave function in atomic photoionization. Using a combination of a strong circularly polarized second harmonic and a weak linearly polarized fundamental field, we spatiotemporally modulate the atomic potential barrier and shape the electron wave functions, which are mapped into a temporal interferometry. By analyzing the two-color phase-resolved and angle-resolved photoelectron interference, we are able to reconstruct the spatiotemporal evolution of the shaping on the amplitude and phase of electron wave function in momentum space within the optical cycle, from which we identify the quantum nature of strong-field ionization and reveal the effect of the spatiotemporal properties of atomic potential on the departing electron. This study provides a new approach for spatiotemporal shaping and imaging of electron wave function in intense light-matter interactions and holds great potential for resolving ultrafast electronic dynamics in molecules, solids, and liquids.

Amplification of light pulses with orbital angular momentum (OAM) in nitrogen ions lasing.

Nitrogen ions pumped by intense femtosecond laser pulses give rise to optical amplification in the ultraviolet range. Here, we demonstrated that a seed light pulse carrying orbital angular momentum (OAM) can be significantly amplified in nitrogen plasma excited by a Gaussian femtosecond laser pulse. With the topological charge of ℓ = ±1, we observed an energy amplification of the seed light pulse by two orders of magnitude, while the amplified pulse carries the same OAM as the incident seed pulse. Moreover, we show that a spatial misalignment of the plasma amplifier with the OAM seed beam leads to an amplified emission of Gaussian mode without OAM, due to the special spatial profile of the OAM seed pulse that presents a donut-shaped intensity distribution. Utilizing this misalignment, we can implement an optical switch that toggles the output signal between Gaussian mode and OAM mode. This work not only certifies the phase transfer from the seed light to the amplified signal, but also highlights the important role of spatial overlap of the donut-shaped seed beam with the gain region of the nitrogen plasma for the achievement of OAM beam amplification.

Entangled X-Ray Photon Pair Generation by Free-Electron Lasers.

We investigate entangled x-ray photon pair emissions in a free-electron laser (FEL) and establish a quantum electrodynamical theory for coherently amplified entangled photon pair emission from microbunched electron pulses in the undulator. We provide a scheme to generate highly entangled x-ray photon pairs and numerically demonstrate the properties of entangled emission, which is of great importance in x-ray quantum optics. Our work shows a unique advantage of FELs in entangled x-ray photon pair generation.

Imaging and Controlling Ultrafast Electron Pulses Emitted from Plasmonic Nanostructures.

We experimentally study photoemission from gold nanodisk arrays using space-, time-, and energy-resolved photoemission electron microscopy. When excited by a plasmonic resonant infrared (IR) laser pulse, plasmonic hotspots are generated owing to local surface plasmon resonance. Photoelectrons emitted from each plasmonic hotspot form a nanoscale and ultrashort electron pulse. When the system is excited by an extreme ultraviolet (EUV) laser pulse, a uniformly distributed photoelectron cloud is formed across the sample surface. When excited by the IR and EUV laser pulses together, both the photoemission image and kinetic energy vary significantly for the IR laser-generated electrons depending on the time delay between the two laser pulses. These observations are well explained by the Coulomb interaction with the EUV laser-generated electron cloud. Our study offers a feasible approach to manipulate the energy of electron pulse emitted from a plasmonic nanostructure on an ultrafast time scale.

Geometric Phase Effect in Attosecond Stimulated X-ray Raman Spectroscopy.

Conical intersections (CIs) are diabolical points in the potential energy surfaces generally caused by point-wise degeneracy of different electronic states, and give rise to the geometric phases (GPs) of molecular wave functions. Here we theoretically propose and demonstrate that the transient redistribution of ultrafast electronic coherence in attosecond Raman signal (TRUECARS) spectroscopy is capable of detecting the GP effect in excited state molecules by applying two probe pulses including an attosecond and a femtosecond X-ray pulse. The mechanism is based on a set of symmetry selection rules in the presence of nontrivial GPs. The model of this work can be realized for probing the geometric phase effect in the excited state dynamics of complex molecules with appropriate symmetries, using attosecond light sources such as free-electron X-ray lasers.

Trajectory-controlled high-order harmonic generation in ZnO crystals.

We experimentally and theoretically study high-order harmonic generation in zinc oxide crystals irradiated by mid-infrared lasers. The trajectories are mapped to the far field spatial distribution of harmonics. The divergence angles of on-axis and off-axis parts exhibit different dependences on the order of the harmonics. This observation can be theoretically reproduced by the coherent interference between the short and long trajectories with dephasing time longer than 0.5 optical cycle. Further, the relative contribution of the short and long trajectories is demonstrated to be accurately controlled by a one-color or two-color laser on the attosecond time scale. This work provides a reliable method to determine the electron dephasing time and demonstrates a versatile control of trajectory interference in the solid high-order harmonic generation.

Holistic quality evaluation of Callicarpae Formosanae Folium by multi-chromatography-based qualitative and quantitative analysis of polysaccharides and small molecules.

Callicarpae Formosanae Folium (CFF), derived from the leaves of Callicarpa formosana Rolfe, is a common Chinese medicinal herb used for the treatment of hematemesis. Phytochemical studies found that phenylpropanoids, flavonoids, terpenoids and polysaccharides were the main ingredients of CFF. However, there is limited scientific information concerning holistic quality method and quality consistency evaluation of CFF. In this study, a strategy integrating HPGPC-ELSD, HPLC-PDA, UV-VIS and UPLC-QTOF-MS/MS was firstly developed to simultaneously qualify and quantify polysaccharides, as well as representative small molecules in CFF. HPGPC-ELSD was applied to characterize the molecular weight distribution of polysaccharides, HPLC-PDA was developed to qualitatively and quantitatively determine monosaccharides. UV-VIS was used to determine the total polysaccharides content, and UPLC-QTOF-MS/MS was established to characterize the small molecules. The quality consistency of commercial CFF (CM-CFF) was also evaluated. It was shown that the relative molecular weights, the compositional monosaccharides and small molecules composition in CM-CFF and self-collected CFF (SC-CFF) samples were similar. A total of 32 small molecules including 6 phenylpropanoids, 7 flavonoids and 19 terpenoids were characterized in CFF. However, the variation was observed in the content of polysaccharides, luteolin, ursolic acid, as well as total contents of terponoids in CM-CFF samples, which implied that the holistic quality of CM-CFF was inconsistent. The results suggested that the proposed evaluation strategy could be applied as a potential approach for the quality control of CFF. And the quality of CM-CFF should be improved by Good Agriculture Practice (GAP) base and standard processing method.

Effect of harvest time span on physicochemical properties, antioxidant, antimicrobial, and anti-inflammatory activities of Meliponinae honey.

BACKGROUND: The maturity of honey has a great impact on its quality and contents. Additionally, stingless bee honey contains high moisture, which allows microorganisms to survive and ferment, contributing to honey's variable flavor and physicochemical properties. Therefore, there is a need for better quality control of the honey process, especially the harvest time of honey. RESULTS: We gathered honey from the nest of stingless bees Heterotrigona itama and Tetrigona binghami over different time periods, i.e. 15, 30, and 45 days. The results show harvest time considerably affects the physicochemical properties, antioxidant activity, and antimicrobial activity of honey. Good antioxidant activity and antimicrobial activity can be found in honey produced from a longer harvest time. Compared with 15-day harvest time, at 30- or 45-day harvest time water, trehalulose, and protein content and total acidity increased, and the content of reducing sugars, fructose and glucose, and pH values, decreased in both types of honey. Moreover, compared with 15-day harvest time, the sum of six organic acids in the 45-day honey of H. itama fluctuated between 2.78 to 4.12 g 100 g-1 and in the 45-day honey of T. binghami increased from 1.66 to 3.61 g 100 g-1 , respectively. CONCLUSION: Honey harvest time had a significant effect on the physicochemical properties, antioxidant activity, and antimicrobial activity of stingless bee honey (H. itama or T. binghami). This study provides a reference for beekeepers to adjust harvest time to obtain honey with suitable physicochemical parameters. © 2022 Society of Chemical Industry.

Ultrafast extreme ultraviolet photoemission electron microscope.

Here, we report our newly built table-top ultrafast extreme ultraviolet (EUV) photoemission electron microscope. The coherent ultrafast EUV light is served by a single order harmonic, which is generated by the interaction between the intense 800-nm femtosecond laser and noble gases in the hollow core fiber. The required order of the harmonic is selected out by a single grating in the off-plane mount and focused on the sample in the ultrahigh vacuum chamber of the photoemission electron microscope. Using metal gold and copper samples, the spatial resolution is calibrated to be better than 50 nm and the energy resolution is calibrated to be better than 300 meV. This microscope provides an advanced tool for studying electron dynamics covering the full Brillouin zone of solid materials with ultrahigh time, space, and energy resolution.

Probing the Spin-Orbit Time Delay of Multiphoton Ionization of Kr by Bicircular Fields.

We study multiphoton ionization of Kr atoms by circular 400-nm laser fields and probe its photoelectron circular dichroism with the weak corotating and counterrotating circular fields at 800 nm. The unusual momentum- and energy-resolved photoelectron circular dichroisms from the ^{2}P_{1/2} ionic state are observed as compared with those from ^{2}P_{3/2} ionic state. We identify an anomalous ionization enhancement at sidebands related to the ^{2}P_{1/2} ionic state on photoelectron momentum distribution when switching the relative helicity of the two fields from corotating to counterrotating. By performing the two-color intensity-continuously-varying experiments and the pump-probe experiment, we find a specific mixed-photon populated resonant transition channel in counterrotating fields that contributes to the ionization enhancement. We then probe the time delay between the two spin-orbit coupled ionic states (^{2}P_{1/2} and ^{2}P_{3/2}) using bicircular fields and reveal that the resonant transition has an insignificant effect on the relative spin-orbit time delay.

Optical amplification from high vibrational states of ionized nitrogen molecules generated by 800-nm femtosecond laser pulses.

We experimentally investigated the interaction between nitrogen molecules and intense femtosecond laser pulses. When irradiated by an 800-nm pump laser and a delayed 355-nm seed laser, the spectral lines around 353.3 nm and 353.8 nm are observed to be greatly amplified, no matter whether the pump laser is circularly or linearly polarized. The two spectral lines correspond to the transition of N2+ (B, ν' = 5 → X, ν = 4) and N2+ (B, ν' = 4 → X, ν = 3), respectively. In comparison with the spectral lines related with ground vibrational states of nitrogen molecular ion, the observed amplification exhibits different polarization dependence of the pump laser. This distinctive change can be explained by the population variation of high vibrational states caused by the pump laser with different polarizations.

Photon retention in coherently excited nitrogen ions.

Quantum coherence in quantum optics is an essential part of optical information processing and light manipulation. Alkali metal vapors, despite the numerous shortcomings, are traditionally used in quantum optics as a working medium due to convenient near-infrared excitation, strong dipole transitions and long-lived coherence. Here, we proposed and experimentally demonstrated photon retention and subsequent re-emittance with the quantum coherence in a system of coherently excited molecular nitrogen ions (N2+) which are produced using a strong 800 nm femtosecond laser pulse. Such photon retention, facilitated by quantum coherence, keeps releasing directly-unmeasurable coherent photons for tens of picoseconds, but is able to be read out by a time-delayed femtosecond pulse centered at 1580 nm via two-photon resonant absorption, resulting in a strong radiation at 329.3 nm. We reveal a pivotal role of the excited-state population to transmit such extremely weak re-emitted photons in this system. This new finding unveils the nature of the coherent quantum control in N2+ for the potential platform for optical information storage in the remote atmosphere, and facilitates further exploration of fundamental interactions in the quantum optical platform with strong-field ionized molecules..

Ramsey interferometry through coherent A2Πu-X2Σg+-B2Σu+ coupling and population transfer in N2+ air laser.

Motivated by the hot debate on the mechanism of laser-like emission at 391 nm from N2 gas irradiated by a strong 800 nm pump laser and a weak 400 nm seed laser, we theoretically study the temporal profile, optical gain, and modulation of the 391 nm signal from N2+. Our calculation sheds light on the long standing controversy on whether population inversion is indispensable for optical gain and show the Ramsey fringes of the emission intensity at 391 nm formed by additionally injecting another 800 nm pump or 400 nm seed, which provides strong evidence for the coherence driven modulation of transition dipole moment and population transfer between the A2Πu(ν=2)-X2Σg+ states and the B2Σu+(ν=0)-X2Σg+ states. Our results show that the 391 nm optical gain is susceptible to the population inversion within N2+ states manipulated by the Ramsey technique and thus clearly reveal their symbiosis. This study reveals not only the physical picture of producing N2+ population inversion but also versatile control of the N2+ air laser.

Formation Mechanism of Excited Neutral Nitrogen Molecules Pumped by Intense Femtosecond Laser Pulses.

Backward amplified spontaneous emission of neutral nitrogen molecules has been reported from laser-induced plasma filaments. The cavity-free UV emission has great potential applications in remote atmospheric sensing. However, the formation mechanism for the excited nitrogen molecules inside filaments remains controversial. Here we study the formation mechanism of excited nitrogen molecules pumped by intense femtosecond laser pulses. After modification of the electron energy distribution by inclusion of the recollision between the electron and its parent ion as well as modification of the electron collision cross section by inclusion of the secondary electron contribution, the theoretical calculations reproduce the experimental observations very well. The results clearly demonstrate that excited nitrogen molecules are generated through collisions between energetic electrons and neutral nitrogen molecules.

Enhanced Coherent Emission from Ionized Nitrogen Molecules by Femtosecond Laser Pulses.

The forward emission spectra were experimentally measured for ionized nitrogen molecules by an 800 nm pump laser and a delayed seed laser. It was found that emission lines around both 428 and 391 nm are greatly enhanced upon use of a 391 or 428 nm seed laser. The emission lines around 391 and 428 nm can be assigned to the rotational transitions of N2+ [B2Σu+(v' = 0) → X2Σg+(v = 0)] and N2+ [B2Σu+(v' = 0) → X2Σg+(v = 1)], respectively. They originate from seed-induced superfluorescence and resonant stimulated Raman scattering. The genetic algorithm was utilized to simulate the experimental observations and determine the relative population of B2Σu+(v' = 0), X2Σg+(v = 1), and X2Σg+(v = 0). The result verifies that vibrational population inversion is achieved between B2Σu+(v' = 0) and X2Σg+(v = 0) by the 800 nm pump laser. Our finding provides new insights into controlling the coherent emission of ionized nitrogen molecules, which has promising application in filamentation-based remote atmospheric sensing.