Correlated electron-nuclear dynamics of photoinduced water dissociation on rutile TiO2.

Elucidating the mechanism of photoinduced water splitting on TiO2 is important for advancing the understanding of photocatalysis and the ability to control photocatalytic surface reactions. However, incomplete experimental information and complex coupled electron-nuclear motion make the microscopic understanding challenging. Here we analyse the atomic-scale pathways of photogenerated charge carrier transport and photoinduced water dissociation at the prototypical water-rutile TiO2(110) interface using first-principles dynamics simulations. Two distinct mechanisms are observed. Field-initiated electron migration leads to adsorbed water dissociation via proton transfer to a surface bridging oxygen. In the other pathway, adsorbed water dissociation occurs via proton donation to a second-layer water molecule coupled to photoexcited-hole transfer promoted by in-plane surface lattice distortions. Two stages of non-adiabatic in-plane lattice motion-expansion and recovery-are observed, which are closely associated with population changes in Ti3d orbitals. Controlling such highly correlated electron-nuclear dynamics may provide opportunities for boosting the performance of photocatalytic materials.

Three-stage ultrafast demagnetization dynamics in a monolayer ferromagnet.

Intense laser pulses can be used to demagnetize a magnetic material on an extremely short timescale. While this ultrafast demagnetization offers the potential for new magneto-optical devices, it poses challenges in capturing coupled spin-electron and spin-lattice dynamics. In this article, we study the photoinduced ultrafast demagnetization of a prototype monolayer ferromagnet Fe3GeTe2 and resolve the three-stage demagnetization process characterized by an ultrafast and substantial demagnetization on a timescale of 100 fs, followed by light-induced coherent A1g phonon dynamics which is strongly coupled to the spin dynamics in the next 200-800 fs. In the third stage, chiral lattice vibrations driven by nonlinear phonon couplings, both in-plane and out-of-plane are produced, resulting in significant spin precession. Nonadiabatic effects are found to introduce considerable phonon hardening and suppress the spin-lattice couplings during demagnetization. Our results advance our understanding of dynamic charge-spin-lattice couplings in the ultrafast demagnetization and evidence angular momentum transfer between the phonon and spin degrees of freedom.

Solid-state high harmonic spectroscopy for all-optical band structure probing of high-pressure quantum states.

High pressure has triggered various novel states/properties in condensed matter, as the most representative and dramatic example being near-room-temperature superconductivity in highly pressured hydrides (~200 GPa). However, the mechanism of superconductivity is not confirmed, due to the lacking of effective approach to probe the electronic band structure under such high pressures. Here, we theoretically propose that the band structure and electron-phonon coupling (EPC) of high-pressure quantum states can be probed by solid-state high harmonic generation (sHHG). This strategy is investigated in high-pressure Im-3m H3S by the state-of-the-art first-principles time-dependent density-functional theory simulations, where the sHHG is revealed to be strongly dependent on the electronic structures and EPC. The dispersion of multiple bands near the Fermi level is effectively retrieved along different momentum directions. Our study provides unique insights into the potential all-optical route for band structure and EPC probing of high-pressure quantum states, which is expected to be helpful for the experimental exploration of high-pressure superconductivity in the future.

Molecular Orbital Insights into Plasmon-Induced Methane Photolysis.

As a promising way to reduce the temperature for conventional thermolysis, plasmon-induced photocatalysis has been utilized for the dehydrogenation of methane. Here we probe the microscopic dynamic mechanism for plasmon-induced methane dissociation over a tetrahedral Ag20 nanoparticle with molecular orbital insights using time-dependent density functional theory. We ingeniously built the relationship between the chemical bonds and molecular orbitals via Hellmann-Feynman forces. The time- and energy-resolved photocarrier analysis shows that the indirect hot hole transfer from the Ag nanoparticle to methane dominates the photoreaction at low laser intensity, due to the strong hybridization of the Ag nanoparticle and CH4 orbitals, while indirect and direct charge transfer coexist to facilitate methane dissociation in intense laser fields. Our findings can be used to design novel methane photocatalysts and highlight the broad prospects of the molecular orbital approach for adsorbate-substrate systems.

Unraveling Hidden Charge Density Wave Phases in 1T-TiSe_{2}.

The unexpected chiral order observed in 1T-TiSe_{2} represents an exciting area to explore chirality in condensed matter, while its microscopic mechanism remains elusive. Here, we have identified three metastable collective modes-the so-called single-q modes-in single layer TiSe_{2}, which originate from the unstable phonon eigenvectors at the zone boundary and break the threefold rotational symmetry. We show that polarized laser pulse is a unique and efficient tool to reconstruct the transient potential energy surface, so as to drive phase transitions between these states. By designing sequent layers with chiral stacking order, we propose a practical means to realize chiral charge density waves in 1T-TiSe_{2}. Further, the constructed chiral structure is predicted to exhibit circular dichroism as observed in recent experiments. These facts strongly indicate the chirality transfer from photons to the electron subsystem, meanwhile being strongly coupled to the lattice degree of freedom. Our work provides new insights into understanding and modulating chirality in quantum materials that we hope will spark further experimental investigation.

Coherent-Phonon-Driven Intervalley Scattering and Rabi Oscillation in Multivalley 2D Materials.

Resolving the complete electron scattering dynamics mediated by coherent phonons is crucial for understanding electron-phonon couplings beyond equilibrium. Here we present a time-resolved theoretical investigation on strongly coupled ultrafast electron and phonon dynamics in monolayer WSe_{2}, with a focus on the intervalley scattering from the optically "bright" K state to "dark" Q state. We find that the strong coherent lattice vibration along the longitudinal acoustic phonon mode [LA(M)] can drastically promote K-to-Q transition on a timescale of ∼400 fs, comparable with previous experimental observation on thermal-phonon-mediated electron dynamics. Further, this coherent-phonon-driven intervalley scattering occurs in an unconventional steplike manner and further induces an electronic Rabi oscillation. By constructing a two-level model and quantitatively comparing with ab initio dynamic simulations, we uncover the critical role of nonadiabatic coupling effects. Finally, a new strategy is proposed to effectively tune the intervalley scattering rates by varying the coherent phonon amplitude, which could be realized via light-induced nonlinear phononics that we hope will spark experimental investigation.

Giant acceleration of polaron transport by ultrafast laser-induced coherent phonons.

Polaron formation is ubiquitous in polarized materials, but severely hampers carrier transport for which effective controlling methods are urgently needed. Here, we show that laser-controlled coherent phonon excitation enables orders of magnitude enhancement of carrier mobility via accelerating polaron transport in a prototypical material, lithium peroxide (Li2O2). The selective excitation of specific phonon modes, whose vibrational pattern directly overlap with the polaronic lattice deformation, can remarkably reduce the energy barrier for polaron hopping. The strong nonadiabatic couplings between the electronic and ionic subsystem play a key role in triggering the migration of polaron, via promoting phonon-phonon scattering in q space within sub-picoseconds. These results extend our understanding of polaron transport dynamics to the nonequilibrium regime and allow for optoelectronic devices with ultrahigh on-off ratio and ultrafast responsibility, competitive with those of state-of-the-art devices fabricated based on free electron transport.

Why Does Single-Atom Photocatalysis Work Better Than Conventional Photocatalysis? A Study on Ultrafast Excited Carrier and Structure Dynamics.

With the introduction of single atoms in photocatalysis, a small change in the electronic and geometric structure of the substrate can result in higher energy conversion efficiency, whereas the underlying microscopic dynamics are rarely illustrated. Here, employing real-time time-dependent density functional theory, we explore the ultrafast electronic and structural dynamics of single-atom photocatalysts (SAPCs) in water splitting at the microscopic scale. The results demonstrate that a single-atom Pt loaded on graphitic carbon nitride greatly promotes photogenerated carriers compared to traditional photocatalysts, and effectively separates the excited electrons from holes, prolonging the lifetime of the excited carriers. The flexible oxidation state (Pt2+, Pt0, or Pt3+) renders the single atom as an active site to adsorb the reactant and to catalyze the reactions as a charge transfer bridge at different stages during the photoreaction process. Our results offer deep insights into the single-atom photocatalytic reactions and benefit the design of high-efficiency SAPCs.

Coherent Phonon Assisted Ultrafast Order-Parameter Reversal and Hidden Metallic State in Ta_{2}NiSe_{5}.

The nonequilibrium dynamics during photoinduced insulator-to-metal transition (IMT) in the excitonic insulator (EI) candidate Ta_{2}NiSe_{5} have been investigated, which reproduce the timescale and spectral features of the ultrafast switch and reveal intricate many-body interactions involving multidegrees of freedom. The key role of lattice order parameter (OP) reversal, occurring on a timescale comparable to that of purely electronic processes (<100 fs), is identified. This reversal is enabled by the anharmonic interactions between EI-OP-coupled phonons and the conventional coherent phonons, leading to a modified potential energy landscape and a high-frequency mode up-conversion. The phonon excitation depends on the dynamics of photocarriers distributed around the Fermi level, and thus intertwines with the excitonic quenching and the complete gap collapse. These findings provide a comprehensive understanding of exciton-phonon dynamics in correlated quantum materials.

Decoupled ultrafast electronic and structural phase transitions in photoexcited monoclinic VO2.

Photoexcitation has emerged as an efficient way to trigger phase transitions in strongly correlated materials. There are great controversies about the atomistic mechanisms of structural phase transitions (SPTs) from monoclinic (M1-) to rutile (R-) VO2 and its association with electronic insulator-metal transitions (IMTs). Here, we illustrate the underlying atomistic processes and decoupling nature of photoinduced SPT and IMT in nonequilibrium states. The photoinduced SPT proceeds in the order of dilation of V-V pairs and increase of twisting angles after a small delay of ~40 fs. Dynamic simulations with hybrid functionals confirm the existence of isostructural IMT. The photoinduced SPT and IMT exhibit the same thresholds of electronic excitations, indicating similar fluence thresholds in experiments. The IMT is quasi-instantaneously (<10 fs) generated, while the SPT takes place with time a constant of 100 to 300 fs. These findings clarify some key controversies in the literature and provide insights into nonequilibrium phase transitions in correlated materials.

Calibrating Out-of-Equilibrium Electron-Phonon Couplings in Photoexcited MoS2.

Nonequilibrium electron-phonon coupling (EPC) serves as a dominant interaction in a multitude of transient processes, including photoinduced phase transitions, coherent phonon generation, and possible light-induced superconductivity. Here we use monolayer MoS2 as a prototype to investigate the variation in electron-phonon couplings under laser excitation, on the basis of real-time time-dependent density functional theory simulations. Phonon softening, anisotropic modification of the deformation potential, and enhancement of EPC are observed, which are attributed to the reduced electronic screening and modulated potential energy surfaces by photoexcitation. Furthermore, by tracking the transient deformation potential and nonthermal electronic population, we can monitor the ultrafast time evolution of the energy exchange rate between electrons and phonons upon laser excitation. This work provides an effective strategy to investigate the nonequilibrium EPC and constructs a scaffold for understanding nonequilibrium states beyond the multitemperature models.

Optical Control of Multistage Phase Transition via Phonon Coupling in MoTe_{2}.

The temporal characters of laser-driven phase transition from 2H to 1T^{'} has been investigated in the prototype MoTe_{2} monolayer. This process is found to be induced by fundamental electron-phonon interactions, with an unexpected phonon excitation and coupling pathway closely related to the nonequilibrium relaxation of photoexcited electrons. The order-to-order phase transformation is dissected into three substages, involving energy and momentum scattering processes from optical (A_{1}^{'} and E^{'}) to acoustic phonon modes [LA(M)] in subpicosecond timescale. An intermediate metallic state along the nonadiabatic transition pathway is also identified. These results have profound implications on nonequilibrium phase engineering strategies.

Indirect to Direct Charge Transfer Transition in Plasmon-Enabled CO2 Photoreduction.

Understanding hot carrier dynamics between plasmonic nanomaterials and its adsorbate is of great importance for plasmon-enhanced photoelectronic processes such as photocatalysis, optical sensing and spectroscopic analysis. However, it is often challenging to identify specific dominant mechanisms for a given process because of the complex pathways and ultrafast interactive dynamics of the photoelectrons. Here, using CO2 reduction as an example, the underlying mechanisms of plasmon-driven catalysis at the single-molecule level using time-dependent density functional theory calculations is clearly probed. The CO2 molecule adsorbed on two typical nanoclusters, Ag20 and Ag147 , is photoreduced by optically excited plasmon, accompanied by the excitation of asymmetric stretching and bending modes of CO2 . A nonlinear relationship has been identified between laser intensity and reaction rate, demonstrating a synergic interplay and transition from indirect hot-electron transfer to direct charge transfer, enacted by strong localized surface plasmons. These findings offer new insights for CO2 photoreduction and for the design of effective pathways toward highly efficient plasmon-mediated photocatalysis.

Plasmon-Induced Water Splitting on Ag-Alloyed Pt Single-Atom Catalysts.

A promising route to realize solar-to-chemical energy conversion resorts to water splitting using plasmon photocatalysis. However, the ultrafast carrier dynamics and underlying mechanism in such processes has seldom been investigated, especially when the single-atom catalyst is introduced. Here, from the perspective of quantum dynamics at the atomic length scale and femtosecond time scale, we probe the carrier and structural dynamics of plasmon-assisted water splitting on an Ag-alloyed Pt single-atom catalyst, represented by the Ag19Pt nanocluster. The substitution of an Ag atom by the Pt atom at the tip of the tetrahedron Ag20 enhances the interaction between water and the nanoparticle. The excitation of localized surface plasmons in the Ag19Pt cluster strengthens the charge separation and electron transfer upon illumination. These facts cooperatively turn on more than one charge transfer channels and give rise to enhanced charge transfer from the metal nanoparticle to the water molecule, resulting in rapid plasmon-induced water splitting. These results provide atomistic insights and guidelines for the design of efficient single-atom photocatalysts for plasmon-assisted water splitting.

Nonadiabatic Dynamics of Photocatalytic Water Splitting on A Polymeric Semiconductor.

To elucidate the nature of light-driven photocatalytic water splitting, a polymeric semiconductor-graphitic carbon nitride (g-C3N4)-has been chosen as a prototype substrate for studying atomistic water spitting processes in realistic environments. Our nonadiabatic quantum dynamics simulations based on real-time time-dependent density functional theory reveal explicitly the transport channel of photogenerated charge carriers at the g-C3N4/water interface, which shows a strong correlation to bond re-forming. A three-step photoreaction mechanism is proposed, whereas the key roles of hole-driven hydrogen transfer and interfacial water configurations were identified. Immediately following photocatalytic water splitting, atomic pathways for the two dissociated hydrogen atoms approaching each other and forming the H2 gas molecule are demonstrated, while the remanent OH radicals may form intermediate products (e.g., H2O2). These results provide critical new insights for the characterization and further development of efficient water-splitting photocatalysts from a dynamic perspective.

Probing Laser-Induced Plasma Generation in Liquid Water.

Understanding photoexcitation dynamics in liquid water is of crucial significance for both fundamental scientific exploration and technological applications. Despite the observations of photoinduced macroscopic phenomena, the initial atomistic movements and associated energy transfer pathways immediately following laser irradiation are hard to track due to the extreme complexity of laser-water interaction and its ultrafast time scale. We explore the femtosecond evolution of liquid water upon intense photoexcitation based on nonadiabatic quantum dynamics simulations. Separate ionic and electronic dynamics were explicitly monitored with tremendous details unveiled on an unprecedented microscopic level. Water was found to undergo the two-step heating processes. The strong-field effects and electronic excitations dominate the first-stage heating and pressurization. Subsequent relaxation of ionic and electronic subsystems further increases the ionic temperature but releases the large internal pressure. The water molecules are stretched during the laser pulses, and the electronic excitations result in the proton transfers after laser pulses. Intense laser pulses violently excite liquid water, giving rise to severe molecular dissociation and plasma generation during the laser pulses. The laser-induced water plasma is characterized by a high fraction of free protons (∼50%), nonequilibrium ionic and electronic distributions, and a metallic electronic density of states.

[Development of a New-type Nail-fold Microcirculation Imaging Device].

At present, there are many problems in the nail-fold microcirculation detection devices, such as huge structure, inconvenience to carry. In addition, due to the patient's body shaking, the video is difficult to keep stable in collecting with the device, which brings great difficulties to the doctor's observation. We develop a small image acquisition device for nail-fold microcirculation based on the principle of SDF imaging principle and liquid lenses technology. An annular lighting device is fixed in front of the optical system, and the overall design of the system is based on the characteristics of human fingers. The device is small, easy to carry and conform to the fingertips. It can focus quickly through a controller. It can also achieve high quality images of the nail-fold microcirculation. This study can promote the usage of nail-fold microcirculation device at the bedside. It's an efficient tool for medical workers to observe the microcirculation of patients.

Impact of CHRNA5 polymorphisms on the risk of schizophrenia in the Chinese Han population.

BACKGROUND: Schizophrenia is a complex mental disease whose cause is still unknown. Neuronal nicotinic acetylcholine receptors (nAChRs) have been implicated in various neurological disorders, including schizophrenia. The previous reports have shown that CHRNA polymorphisms were involved in schizophrenia. This study is to explore the potential association between CHRNA5 (OMIM#118505) polymorphisms and schizophrenia susceptibility in a Chinese population. METHODS AND RESULTS: A case-control study was conducted with 384 schizophrenia patients and 687 controls. We genotyped eight single nucleotide polymorphisms (SNPs) distributed in CHRNA5. Regulome DB, HaploReg, and GTEx databases were used to calculate possible functional effects of the polymorphisms. The χ2 test, genetic model analysis, and haplotype analysis were involved in assessing genetic association between variants and schizophrenia risk. The results exhibited that rs17486278 (NC_000015.10:g.78575140A>C) was associated with a decreased risk of schizophrenia on the basis of the recessive model (adjusted OR = 0.37, 95%CI: 0.15-0.93) in females. Moreover, we found that the four variants rs588765, rs6495306, rs680244, rs692780 were extremely significant after being stratified by ≥45 years. CONCLUSIONS: Overall, our findings supported that the potential association existed between CHRNA5 polymorphisms and schizophrenia susceptibility in a Chinese population. But, large sample validation is needed to enhance the accuracy of our results.

[Comparison study on diagnostic and prognostic value of N-terminal probrain natriuretic peptide and atrium natriuretic peptide in chronic congestive heart failure].

OBJECTIVE: To investigate the diagnostic and prognostic value of N-terminal probrain natriuretic peptide(NT-proBNP)and atrium natriuretic peptide(ANP)in chronic congestive heart failure. METHODS: One hundred and eighteen coronary heart disease patients were enrolled in the study. Among them 78 patients were accompanied by heart failure and 40 with no heart failure. Plasma NT-proBNP was determined with Elecsys Chemiluminescence Immunoassay method, and plasma ANP was determined with radioimmunoassay method.The results were compared with those of 40 healthy individuals. All patients were followed up accordingly. RESULTS: Compared with patients with no heart failure and healthy individuals, the patients with heart failure had a higher plasma NT-proBNP and ANP contents(P<0.05). Cardiac function grade IV patients had a significantly higher plasma NT-proBNP than cardiac function grade II and III patients, and their plasma ANP level was significanthy higher than that of cardiac function grade III patients, but there was no significantly difference in ANP content between cardiac function grade IV and II.The diagnostic sensitivity of NT-proBNP and ANP was 91.25% and 73.46%, respectively. The diagnostic specificity of NT-proBNP and ANP was 90.25%, 80.33%, respectively. In the heart failure group, it was found that there was no significant difference in the plasma NT-proBNP and ANP between the deaths and surviving patients. CONCLUSION: The diagnostic value of NT-proBNP in chronic heart failure is higher than that of ANP. According to our follow- up result, the plasma NT-proBNP and ANP can not be relied up on to predict short -term cardiogenic death in heart failure.

[Age- and gender-related changes of biochemical markers for bone metabolic turnover].

OBJECTIVE: To investigate the age- and gender-related changes in serum biochemical markers for bone metabolic turnover to establish the reference ranges for these markers for osteoporosis prevention and monitoring. METHODS: In 276 healthy individuals, serum type I collagen C-telopeptide (beta-Crosslaps), osteocalin and alkaline phosphatase levels were measured by electrochemiluminescence immunoassay, radioimmunoassay and consecutive monitoring, respectively. RESULTS: No significant changes in serum phosphatase was found in relation to age and gender. Serum beta-crosslaps levels tended to increase with age in male and female subjects, but only until the age of 50-59 years, such changes began to be statistically significant (P<0.05) as compared with the levels in the youngest group. Above this age range, beta-crosslaps level in female subjects increased dramatically, showing significant difference between adjacent age groups (P<0.05), which, however, was out observed in male subjects. Serum osteocalin level was lowered with age in female subjects before the age of 50 years, but a significant increase occurred at the age of 50-59 years (P<0.05) followed by a relatively stable and mild increase that did not result in significant difference between adjacent age groups. In male subjects, serum osteocalin level reached the peak level at the age of 30-39 years followed by stable and mild decrease with age. The ratio of beta-crosslaps/osteocalin tended to increase with age in both male and female subjects. CONCLUSION: There are age- and gender-related changes in serum beta-crosslaps, osteocalin and especially beta-crosslaps/osteocalin ratio, suggesting the value of testing serum beta-crosslaps and osteocalin in the prevention and treatment of osteoporosis.