Structures,Energetics, and Infrared Spectra of the Cationic Monomethylamine-Water Clusters

The structures, energetics, and infrared (IR) spectra of the cationic monomethylamine-water clusters, [(CH\begin{document}$_3$\end{document}NH\begin{document}$_2$\end{document})(H\begin{document}$_2$\end{document}O)\begin{document}$_n$\end{document}]\begin{document}$^+$\end{document} (\begin{document}$n$\end{document}=1\begin{document}$-$\end{document}5), have been studied using quantum chemical calculations at the MP2/6-311+G(2d,p) level. The results reveal that the formation of proton-transferred CH\begin{document}$_2$\end{document}NH\begin{document}$_3$\end{document}\begin{document}$^+$\end{document} ion core structure is preferred via the intramolecular proton transfer from the methyl group to the nitrogen atom and the water molecules act as the acceptor for the O\begin{document}$\cdots$\end{document}HN hydrogen bonds with the positively charged NH\begin{document}$_3$\end{document}\begin{document}$^+$\end{document} moiety of CH\begin{document}$_2$\end{document}NH\begin{document}$_3$\end{document}\begin{document}$^+$\end{document}, whose motif is retained in the larger clusters. The CH\begin{document}$_3$\end{document}NH\begin{document}$_2$\end{document}\begin{document}$^+$\end{document} ion core structure is predicted to be less energetically favorable. Vibrational frequencies of CH stretches, hydrogen-bonded and free NH stretches, and hydrogen-bonded OH stretches in the calculated IR spectra of the CH\begin{document}$_2$\end{document}NH\begin{document}$_3$\end{document}\begin{document}$^+$\end{document} and CH\begin{document}$_3$\end{document}NH\begin{document}$_2$\end{document}\begin{document}$^+$\end{document} type structures are different from each other, which would afford the sensitive probes for fundamental understanding of hydrogen bonding networks generated from the radiation-induced chemical processes in the [(CH\begin{document}$_3$\end{document}NH\begin{document}$_2$\end{document})(H\begin{document}$_2$\end{document}O)\begin{document}$_n$\end{document}]\begin{document}$^+$\end{document} complexes.     

Theoretical study of the adsorption of silver atoms on the (111) face of silicon

The adsorption of one or many silver atoms on a (111) silicon face (reduced to 61 dangling atomic orbitals) is investigated by means of a self-consistent Hartree–Fock method parametrized from atomic and thermodynamical data. The valley sites (above three Si atoms) are favored over the top sites (above one Si atom). The extrapolation of the results obtained for several structures corresponding to the adsorption of n = 1, 2, 3, 4, 6, and 7 Ag atoms allows us to conclude that the most stable structures correspond: for \documentclass{article}\pagestyle{empty}\begin{document}$ \theta = \frac{1}{3} $\end{document} to linear Ag chains (3 × 1 phase), for \documentclass{article}\pagestyle{empty}\begin{document}$ \theta = \frac{2}{3} $\end{document} to an honeycomb lattice (\documentclass{article}\pagestyle{empty}\begin{document}$ \sqrt 3 \times \sqrt 3 $\end{document} phase), and for θ = 1 to a centred hexagonal lattice (\documentclass{article}\pagestyle{empty}\begin{document}$ \sqrt 3 \times \sqrt 3 $\end{document} phase), the Ag atoms located at the centers of the hexagons being beneath the plan of the hexagons. The adsorption energies corresponding to the various θ are practically equal (ca. 3 eV/Ag). The net charges of Ag atoms are equal to 0.35.     

Substituent Effects on the Photocatalytic Properties of a Symmetric Covalent Organic Framework

Symmetric covalent organic framework (COF) photocatalysts generally suffer from inefficient charge separation and short-lived photoexcited states. By performing density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations, we find that partial substitution with one or two substituents (N or NH\begin{document}$_2$\end{document}) in the linkage of the representative symmetric COF (N\begin{document}$_0$\end{document}-COF) gives rise to the separation of charge carriers in the resulting COFs (\emph{i.e}., N\begin{document}$_1$\end{document}-COF, N\begin{document}$_2$\end{document}-COF, (NH\begin{document}$_2$\end{document})\begin{document}$_1$\end{document}-N\begin{document}$_0$\end{document}-COF, and (NH\begin{document}$_2$\end{document})\begin{document}$_2$\end{document}-N\begin{document}$_0$\end{document}-COF). Moreover, we also find that the energy levels of the highest occupied crystal orbital (HOCO) and the lowest unoccupied crystal orbital (LUCO) of the N\begin{document}$_0$\end{document}-COF can shift away from or toward the vacuum level, depending on the electron-withdrawing or electron-donating characters of the substituent. Therefore, we propose that partial substitution with carefully chosen electron-withdrawing or electron-donating substituents in the linkages of symmetric COFs can lead to efficient charge separation as well as appropriate HOCO and LUCO positions of the generated COFs for specific photocatalytic reactions. The proposed rule can be utilized to further boost the photocatalytic performance of many symmetric COFs.     

Accurate Quantum Dynamics of the Simplest Isomerization System Involving Double-H Transfer

We perform accurate quantum dynamics calculations on the isomerization of vinylidene-acetylene. Large-scale parallel computations are accomplished by an efficient theoretical scheme developed by our group, in which the basis functions are customized for the double-H transfer process. The \begin{document}$ A_1' $\end{document} and \begin{document}$ B_2'' $\end{document} vinylidene and delocalization states are obtained. The peaks recently observed in the cryo-SEVI spectra are analyzed, and very good agreement for the energy levels is achieved between theory and experiment. The discrepancies of energy levels between our calculations and recent experimental cryo-SEVI spectra are of similar magnitudes to the experimental error bars, or \begin{document}$ \le $\end{document}30 cm\begin{document}$ ^{-1} $\end{document} excluding those involving the excitation of the CCH\begin{document}$ _2 $\end{document} scissor mode. A kind of special state, called the isomerization state, is revealed and reported, which is characterized by large probability densities in both vinylidene and acetylene regions. In addition, several states dominated by vinylidene character are reported for the first time. The present work would contribute to the understanding of the double-H transfer.     

Ro-vibrational Spectra of the Simplest Deuterated Criegee Intermediate CD2OO

Criegee intermediates are of significance in the atmospheric chemistry. In this work, the ro-vibrational spectra of the simplest deuterated Criegee intermediate, CD\begin{document}$ _2 $\end{document}OO, were studied by a vibrational self-consistent field/virtual configuration interaction (VSCF/VCI) method based on a nine-dimensional accurate potential energy surface and dipole surface for its ground electronic state. The calculated fundamental vibrational frequencies and rotational constants are in excellent agreement with the available experimental results. These data are useful for further spectroscopic studies of CD\begin{document}$ _2 $\end{document}OO. Especially, the rotational constants for excited vibrational levels are essential for experimental spectral assignments. However, the infrared intensities from different resources, including the current computation, the experiment, and previous calculations at the NEVPT2 and B3LYP levels, deviate significantly.     

Photodynamics of Methyl-Vinyl Criegee Intermediate: Different Conical Intersections Govern the Fates of Syn/Anti Configurations

Methyl vinyl ketone oxide, an unsaturated four-carbon Criegee intermediate produced from the ozonolysis of isoprene has been recognized to play a key role in determining the tropospheric OH concentration. It exists in four configurations (\begin{document}$ anti $\end{document}-\begin{document}$ anti $\end{document}, \begin{document}$ anti $\end{document}-\begin{document}$ syn $\end{document}, \begin{document}$ syn $\end{document}-\begin{document}$ anti $\end{document}, and \begin{document}$ syn $\end{document}-\begin{document}$ syn $\end{document}) due to two different substituents of saturated methyl and unsaturated vinyl groups. In this study, we have carried out the electronic structure calculation at the multi-configurational CASSCF and multi-state MS-CASPT2 levels, as well as the trajectory surface-hopping nonadiabatic dynamics simulation at the CASSCF level to reveal the different fates of \begin{document}$ syn $\end{document}/\begin{document}$ anti $\end{document} configurations in photochemical process. Our results show that the dominant channel for the S\begin{document}$ _1 $\end{document}-state decay is a ring closure, isomerization to dioxirane, during which, the \begin{document}$ syn $\end{document}(C\begin{document}$ - $\end{document}O) configuration with an intramolecular hydrogen bond shows slower nonadiabatic photoisomerization. More importantly, it has been found for the first time in photochemistry of Criegee intermediate that the cooperation of two heavy groups (methyl and vinyl) leads to an evident pyramidalization of C3 atom in methyl-vinyl Criegee intermediate, which then results in two structurally-independent minimal-energy crossing points (CIs) towards the \begin{document}$ syn $\end{document}(C\begin{document}$ - $\end{document}O) and \begin{document}$ anti $\end{document}(C\begin{document}$ - $\end{document}O) sides, respectively. The preference of surface hopping for a certain CI is responsible for the different dynamics of each configuration.     

DFT Study on the Catalytic Role of \begin{document}$\alpha$\end{document}-MoC(100) in Methanol Steam Reforming

In this work, we investigated the methanol steam reforming (MSR) reaction (CH\begin{document}$_3$\end{document}OH+H\begin{document}$_2$\end{document}O \begin{document}$\rightarrow$\end{document}CO\begin{document}$_2$\end{document}+3H\begin{document}$_2$\end{document}) catalyzed by \begin{document}$\alpha$\end{document}-MoC by means of density functional theory calculations. The adsorption behavior of the relevant intermediates and the kinetics of the elementary steps in the MSR reaction are systematically investigated. The results show that, on the \begin{document}$\alpha$\end{document}-MoC(100) surface, the O\begin{document}$-$\end{document}H bond cleavage of CH\begin{document}$_3$\end{document}OH leads to CH\begin{document}$_3$\end{document}O, which subsequently dehydrogenates to CH\begin{document}$_2$\end{document}O. Then, the formation of CH\begin{document}$_2$\end{document}OOH between CH\begin{document}$_2$\end{document}O and OH is favored over the decomposition to CHO and H. The sequential dehydrogenation of CH\begin{document}$_2$\end{document}OOH results in a high selectivity for CO\begin{document}$_2$\end{document}. In contrast, the over-strong adsorption of the CH\begin{document}$_2$\end{document}O intermediate on the \begin{document}$\alpha$\end{document}-MoC(111) surface leads to its dehydrogenation to CO product. In addition, we found that OH species, which is produced from the facile water activation, help the O\begin{document}$-$\end{document}H bond breaking of intermediates by lowering the reaction energy barrier. This work not only reveals the catalytic role played by \begin{document}$\alpha$\end{document}-MoC(100) in the MSR reaction, but also provides theoretical guidance for the design of \begin{document}$\alpha$\end{document}-MoC-based catalysts.     

Constrained Density Functional Theory Plus the Hubbard U Correction Approach for the Electronic Polaron Mobility: A Case Study of TiO2?

The formation and migration of polarons have important influences on physical and chemical properties of transition metal oxides. Density functional theory plus the Hubbard \begin{document}$U$\end{document} correction (DFT+\begin{document}$U$\end{document}) and constrained density functional theory (cDFT) are often used to obtain the transfer properties for small polarons. In this work we have implemented the cDFT plus the Hubbard \begin{document}$U$\end{document} correction method in the projector augmented wave (PAW) framework, and applied it to study polaron transfer in the bulk phases of TiO\begin{document}$_2$\end{document}. We have confirmed that the parameter \begin{document}$U$\end{document} can have significant impact on theoretical prediction of polaronic properties. It was found that using the Hubbard \begin{document}$U$\end{document} calculated by the cDFT method with the same orbital projection as used in DFT+\begin{document}$U$\end{document}, one can obtain theoretical prediction of polaronic properties of rutile and anatase phases of TiO\begin{document}$_2$\end{document} in good agreement with experiment. This work indicates that the cDFT+\begin{document}$U$\end{document} method with consistently evaluated \begin{document}$U$\end{document} is a promising first-principles approach to polaronic properties of transition metal oxides without empirical input.     

Roaming Dynamics of H+C\begin{document}$_{2}$\end{document}D\begin{document}$_{2}$\end{document} Reaction on Fundamental-Invariant Neural Network Potential Energy Surface

We performed extensive quasiclassical trajectory calculations for the H+C\begin{document}$_2$\end{document}D\begin{document}$_2$\end{document}\begin{document}$\rightarrow$\end{document}HD+C\begin{document}$_2$\end{document}D/D\begin{document}$_2$\end{document}+C\begin{document}$_2$\end{document}H reaction based on a recently developed, global and accurate potential energy surface by the fundamental-invariant neural network method. The direct abstraction pathway plays a minor role in the overall reactivity, which can be negligible as compared with the roaming pathways. The acetylene-facilitated roaming pathway dominates the reactivity, with very small contributions from the vinylidene-facilitated roaming. Although the roaming pathways proceed via the short-lived or long-lived complex forming process, the computed branching ratio of product HD to D\begin{document}$_2$\end{document} is not far away from 2:1, implying roaming dynamics for this reaction is mainly contributed from the long-lived complex-forming process. The resulting angular distributions for the two product channels are also quite different. These computational results give valuable insights into the significance and isotope effects of roaming dynamics in the biomolecular reactions.     

Direct Observation of Transient Species Generated from Protonation and Deprotonation of the Lowest Triplet of p-Nitrophenylphenol

Photo-induced proton coupled electron transfer (PCET) is essential in the biological, photosynthesis, catalysis and solar energy conversion processes. Recently, \begin{document}$ p $\end{document}-nitrophenylphenol (HO-Bp-NO₂) has been used as a model compound to study the photo-induced PCET mechanism by using ultrafast spectroscopy. In transient absorption spectra both singlet and triplet states were observed to exhibit PCET behavior upon laser excitation of HO-Bp-NO₂. When we focused on the PCET in the triplet state, a new sharp band attracted us. This band was recorded upon excitation of HO-Bp-NO₂ in aprotic polar solvents, and has not been observed for \begin{document}$ p $\end{document}-nitrobiphenyl which is without hydroxyl substitution. In order to find out what the new band represents, acidic solutions were used as an additional proton donor considering the acidity of HO-Bp-NO₂. With the help of results in strong (\begin{document}$ \sim $\end{document}10\begin{document}$ ^{-1} $\end{document} mol/L) and weak (\begin{document}$ \sim $\end{document}10\begin{document}$ ^{-4} $\end{document} mol/L) acidic solutions, the new band is identified as open shell singlet O-Bp-NO₂H, which is generated through protonation of nitro O in \begin{document}$ ^3 $\end{document}HO-Bp-NO₂ followed by deprotonation of hydroxyl. Kinetics analysis indicates that the formation of radical \begin{document}$ \cdot $\end{document}O-Bp-NO₂ competes with O-Bp-NO₂H in the way of concerted electron-proton transfer and/or proton followed electron transfers and is responsible for the low yield of O-Bp-NO₂H. The results in the present work will make it clear how the \begin{document}$ ^3 $\end{document}HO-Bp-NO₂ deactivates in aprotic polar solvents and provide a solid benchmark for the deeply studying the PCET mechanism in triplets of analogous aromatic nitro compounds.     

GW/BSE Nonadiabatic Dynamics Simulations on Excited-State Relaxation Processes of Zinc Phthalocyanine-Fullerene Dyads: Roles of Bridging Chemical Bonds

In this work, we employ electronic structure calculations and nonadiabatic dynamics simulations based on many-body Green function and Bethe-Salpeter equation (GW/BSE) methods to study excited-state properties of a zinc phthalocyanine-fullerene (ZnPc-C\begin{document}$ _{60} $\end{document}) dyad with 6-6 and 5-6 configurations. In the former, the initially populated locally excited (LE) state of ZnPc is the lowest S\begin{document}$ _1 $\end{document} state and thus, its subsequent charge separation is relatively slow. In contrast, in the latter, the S\begin{document}$ _1 $\end{document} state is the LE state of C\begin{document}$ _{60} $\end{document} while the LE state of ZnPc is much higher in energy. There also exist several charge-transfer (CT) states between the LE states of ZnPc and C\begin{document}$ _{60} $\end{document}. Thus, one can see apparent charge separation dynamics during excited-state relaxation dynamics from the LE state of ZnPc to that of C\begin{document}$ _{60} $\end{document}. These points are verified in dynamics simulations. In the first 200 fs, there is a rapid excitation energy transfer from ZnPc to C\begin{document}$ _{60} $\end{document}, followed by an ultrafast charge separation to form a CT intermediate state. This process is mainly driven by hole transfer from C\begin{document}$ _{60} $\end{document} to ZnPc. The present work demonstrates that different bonding patterns (i.e. 5-6 and 6-6) of the C\begin{document}$ - $\end{document}N linker can be used to tune excited-state properties and thereto optoelectronic properties of covalently bonded ZnPc-C\begin{document}$ _{60} $\end{document} dyads. Methodologically, it is proven that combined GW/BSE nonadiabatic dynamics method is a practical and reliable tool for exploring photoinduced dynamics of nonperiodic dyads, organometallic molecules, quantum dots, nanoclusters, etc.     

Influence of superimposed steady shear flow on the dynamic properties of polyethylene melts

Experiments in which an oscillatory shear flow is superimposed on a steady state shear flow were performed on polyethylene melts by the use of a cone and plate type rheogoniometer. The phase difference between oscillatory shear stress and shear strain increases in all cases and for all frequencies with the increase of the superimposed shear rate. Between ω₀, the frequency at which the phase difference is π/2 and the steady shear rate \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \gamma $\end{document}, as found by Booij for polymer solution, the relation ω₀ = 1/2 \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \gamma$\end{document}. holds also for polyethylene melts. The significance of this relation is discussed briefly from the viewpoint that the entanglement density decreases with the increase of the imposed shear rate.     

Effect of Optical Depth on Study of Chemical Properties of Massive Star Forming Clumps

Here we present the study on chemical properties of massive star forming clumps using N\begin{document}$ _2 $\end{document}H\begin{document}$ ^+ $\end{document}(1-0), H\begin{document}$ ^{13} $\end{document}CO\begin{document}$ ^+ $\end{document}(1-0), HCN(1-0) and HN\begin{document}$ ^{13} $\end{document}C(1-0) data from the literature [Astron. Astrophys. 563 , A97 (2014)]. We found that abundances of H\begin{document}$ ^{13} $\end{document}CO\begin{document}$ ^+ $\end{document} and HN\begin{document}$ ^{13} $\end{document}C are affected by H\begin{document}$ _2 $\end{document} column densities. As the median values of these two abundances increase by nearly 10 times from stages A to B, H\begin{document}$ ^{13} $\end{document}CO\begin{document}$ ^+ $\end{document} and HN\begin{document}$ ^{13} $\end{document}C are suitable for tracing the evolution of massive star forming clumps. The order of rapidity in growth of abundances of all the four studied molecules from stages A to B, is H\begin{document}$ ^{13} $\end{document}CO\begin{document}$ ^+ $\end{document}, HCN, HN\begin{document}$ ^{13} $\end{document}C, and N\begin{document}$ _2 $\end{document}H\begin{document}$ ^+ $\end{document}, from the highest to the lowest. Our results suggest that the observing optically thin molecular lines with high angular resolution are necessary to study the chemical evolution of massive star forming clumps.     

Coordinate Bond Breaking Induced by Collapse of Poly(\begin{document}$N$\end{document}-isopropyl acrylamide) as Ligands of a Rare Earth Complex

A novel water-soluble luminescent complex consisting of Eu(ally-dbm)\begin{document}$_3$\end{document}-2Tppo and poly(N-isopropyl acrylamide) (PNIPAM) is synthesized through a series of chemical reactions. The structure of the complex is characterized by TGA, GPC, HNMR, and the thermal-responsive fluorescence of the complex in aqueous solution is investigated. It is found that PNIPAM collapse above the lower critical solution temperature causes the coordination bond breaking, leading to weakening of the fluorescence from Eu\begin{document}$^{3+}$\end{document} and enhancing of the fluorescence from the ligands. When temperature decreases, the fluorescence from Eu\begin{document}$^{3+}$\end{document} is found to boost up and the fluorescence from ligands weakens accordingly. It is deduced from this phenomenon that the ligands re-coordinate with europium ions again along with the temperature decreasing, which is further confirmed by IR measurements. This thermal-responsive fluorescence is of reversibility, which can be used as molecular probes for biological imaging and collapse studying of PNIPAM.     

Effect of a Single Repeat Sequence of the Human Telomere d(TTAGGG) on Structure of Single-Stranded Telomeric DNA d[AGGG(TTAGGG)\begin{document}$_6$\end{document}]

The structures of human telomeric DNA have received much attention due to its significant biological importance. Most studies have focused on G-quadruplex structure formed by short telomeric DNA sequence, but little is known about the structures of long single-stranded telomeric DNAs. Here, we investigated the structure of DNA with a long sequence of d[AGGG(TTAGGG)\begin{document}$_6$\end{document}] (G\begin{document}$_6$\end{document}-DNA) and the effect of a single repeat sequence d(TTAGGG) (G\begin{document}$_{01}$\end{document}-DNA) on the structure of G\begin{document}$_6$\end{document}-DNA using sedimentation velocity technique, polyacrylamide gel electrophoresis, circular dichroism spectroscopy, and UV melting experiments. The results suggest that the G\begin{document}$_6$\end{document}-DNA can form dimers in aqueous solutions and G\begin{document}$_{01}$\end{document}-DNA can form additional G-quadruplex structures by binding to G\begin{document}$_6$\end{document}-DNA. However, G\begin{document}$_{01}$\end{document}-DNA has no effect on the structure of DNA with a sequence of d[AGGG(TTAGGG)\begin{document}$_3$\end{document}] (G\begin{document}$_3$\end{document}-DNA). Our study provides new insights into the structure polymorphism of long human single-stranded telomeric DNA.     

Three-Dimensional Diabatic Potential Energy Surfaces of Thiophenol with Neural Networks

Three-dimensional (3D) diabatic potential energy surfaces (PESs) of thiophenol involving the S\begin{document}$_0$\end{document}, and coupled \begin{document}$^1$\end{document}\begin{document}$\pi\pi^*$\end{document} and \begin{document}$^1$\end{document}\begin{document}$\pi\sigma^*$\end{document} states were constructed by a neural network approach. Specifically, the diabatization of the PESs for the \begin{document}$^1$\end{document}\begin{document}$\pi\pi^*$\end{document} and \begin{document}$^1\pi\sigma^*$\end{document} states was achieved by the fitting approach with neural networks, which was merely based on adiabatic energies but with the correct symmetry constraint on the off-diagonal term in the diabatic potential energy matrix. The root mean square errors (RMSEs) of the neural network fitting for all three states were found to be quite small (\begin{document}$<$\end{document}4 meV), which suggests the high accuracy of the neural network method. The computed low-lying energy levels of the S\begin{document}$_0$\end{document} state and lifetime of the 0\begin{document}$^0$\end{document} state of S\begin{document}$_1$\end{document} on the neural network PESs are found to be in good agreement with those from the earlier diabatic PESs, which validates the accuracy and reliability of the PESs fitted by the neural network approach.     

Ion-Neutral Photofragment Coincidence Imaging of Photodissociation Dynamics of Ionic Species

The recently constructed cryogenic cylindrical ion trap velocity map imaging spectrometer (CIT-VMI) has been upgraded for coincidence imaging of both ionic and neutral photofragments from photodissociation of ionic species. The prepared ions are cooled down in a home-made cryogenic cylindrical ion trap and then extracted for photodissociation experiments. With the newly designed electric fields for extraction and acceleration, the ion beam can be accelerated to more than 4500 eV, which is necessary for velocity imaging of the neutral photofragments by using the position-sensitive imaging detector. The setup has been tested by the 355 nm photodissociation dynamics of the argon dimer cation (Ar\begin{document}$_2$\end{document}\begin{document}$^+$\end{document}). From the recorded experimental images of both neutral Ar and ionic Ar\begin{document}$^+$\end{document} fragments, we interpret velocity resolutions of \begin{document}$\Delta v/v$\end{document}\begin{document}$\approx$\end{document}4.6% for neutral fragments, and \begin{document}$\Delta v/v$\end{document}\begin{document}$\approx$\end{document}1.5% for ionic fragments, respectively.     

Electrosynthesis of Highly Efficient WO\begin{document}$_{3-x}$\end{document}/Graphene (Photo-)Electro- Catalyst by Two-Electrode Electrolysis System for Oxygen Evolution Reaction

Integration of non-noble transition metal oxides with graphene is known to construct high-activity electrocatalysts for oxygen evolution reduction (OER). In order to avoid the complexity of traditional synthesis process, a facile electrochemical method is elaborately designed to engineer efficient WO\begin{document}$_{3-x}$\end{document}/graphene (photo-)electrocatalyst for OER by a two-electrode electrolysis system, where graphite cathode is exfoliated into graphene and tungsten wire anode evolves into V\begin{document}$_\textrm{O}$\end{document}-rich WO\begin{document}$_{3-x}$\end{document} profiting from formed reductive electrolyte solution. Among as-prepared samples, WO\begin{document}$_{3-x}$\end{document}/G-2 shows the best electrocatalytic performance for OER with an overpotential of 320 mV (without iR compensation) at 10 mA/cm\begin{document}$^2$\end{document}, superior to commercial RuO\begin{document}$_2$\end{document} (341 mV). With introduction of light illumination, the activity of WO\begin{document}$_{3-x}$\end{document}/G-2 is greatly enhanced and its overpotential decreases to 290 mV, benefiting from additional reaction path produced by photocurrent effect and extra active sites generated by photogenerated carriers (h\begin{document}$^+$\end{document}). Characterization results indicate that both V\begin{document}$_\textrm{O}$\end{document}-rich WO\begin{document}$_{3-x}$\end{document} and graphene contribute to the efficient OER performance. The activity of WO\begin{document}$_{3-x}$\end{document} for OER is decided by the synergistic effect between V\begin{document}$_\textrm{O}$\end{document} concentration and particle size. The graphene could not only disperse WO\begin{document}$_{3-x}$\end{document} nanoparticles, but also improve the holistic conductivity and promote electron transmission. This work supports a novel method for engineering WO\begin{document}$_{3-x}$\end{document}/graphene composite for highly efficient (photo-)electrocatalytic performance for OER.     

Systematical Study on Photodissociation Dynamics of BrCN from 225 nm to 260 nm

The photodissociation dynamics of Br\begin{document}$ - $\end{document}C bond cleavage for BrCN in the wavelength region from 225 nm to 260 nm has been studied by our homebuilt time-slice velocity-map imaging setup. The images for both of the ground state Br(\begin{document}$ ^{2} {\rm{P}}_{3/2} $\end{document}) and spin-orbit excited Br\begin{document}$ ^* $\end{document}(\begin{document}$ ^{2} {\rm{P}}_{1/2} $\end{document}) channels are obtained at several photodissociation wavelengths. From the analysis of the translational energy release spectra, the detailed vibrational and rotational distributions of CN products have been measured for both of the Br and Br\begin{document}$ ^* $\end{document} channels. It is found that the internal excitation of the CN products for the Br\begin{document}$ ^* $\end{document} channel is colder than that for the Br channel. The most populated vibrational levels of the CN products are \begin{document}$ v $\end{document}=0 and 1 for the Br and Br\begin{document}$ ^* $\end{document} channels, respectively. For the Br channel, the photodissociation dynamics at longer wavelengths are found to be different from those at shorter wavelengths, as revealed by their dramatically different vibrational and rotational excitations of the CN products.