Mixed threefold and fourfold carbon coordination in compressed CO2

Carbon dioxide (CO2) has been recently reported to possess an amorphous form, named "carbonia," structurally similar to other group-IV oxide glasses. By combining ab initio constant pressure molecular dynamics, density-functional perturbation theory, and experimental IR spectra, we show that carbonia, and possibly also phase VI, is not SiO2-like, and that instead it is partially tetrahedral containing also a sizable amount of carbon in threefold coordination, but no sixfold octahedral coordination. Enthalpic considerations suggest that carbonia is a metastable intermediate state of the transformation of molecular CO2 into fully tetrahedral phases.     

Controlling the bonding and band gaps of solid carbon monoxide with pressure

We use a combination of a searching method and first-principles electronic structure calculations to predict novel structures of carbon monoxide (CO) which are energetically more stable than the known structures. The most stable forms of CO at zero pressure consist of metallic polycarbonyl chains with single and double bonds, rather than the familiar triply bonded insulating CO molecules. At pressures >2 GPa the most stable phases are semiconducting and insulating singly bonded three-dimensional framework and layered structures. We also find a molecular Pbcm structure which is more stable than the R3c structure proposed previously for the observed ? phase.     

Stereoselectivity in catalytic reactions: CO oxidation on Pd(100) by rotationally aligned O2 molecules

We report on stereodynamical effects in heterogeneous catalytic reactions as measured by molecular beam-surface experiments. Specifically for CO oxidation on Pd(100) we find that the rotational alignment of the incoming O₂ at low (Θ = 0.04 ML) and at intermediate (Θ_CO = 0.17 ML) CO pre-coverage, causes a higher reactivity of molecules in high and in low helicity states, respectively (corresponding to helicoptering and cartwheeling motion of O₂). In first approximation, at low CO pre-coverage the difference in reactivity is determined by the different location of the O atoms generated in the dissociation process by the different parent molecules, while at intermediate CO pre-coverage the reactivity is influenced also by the different ability of cartwheeling and helicoptering O₂ to penetrate through the CO adlayer. In accord with this the total amount of CO₂ produced is always largest for helicopters which generate supersurface O atoms at least in the low CO pre-coverage limit. A deeper inspection of the data indicates, however, that the dynamics is more complex, two different pathways being present for the reaction with O generated by helicopters and one for O generated by cartwheels. Moreover, cartwheels generated oxygen influences the reactivity of subsequently arriving helicopters.     

Si-CNT循环催化N_2O与CO反应的理论研究

通过非金属催化转化有毒气体来解决环境问题已经成为最有效最有前景的方法.基于密度泛函理论(Density Functional Theory, DFT)研究了Si掺杂碳纳米管(Si-CNT)催化氧化N_2O与CO的反应. N_2O分子更易以直线形式吸附在Si-CNT催化剂上,并分解为N_2和CNT-SiO中间体,对应的活化能垒为2.42 kJ/mol. CNT-SiO中间体很活泼很容易与CO继续反应生成CO_2.通过分析发现CNT既可以作为电子的接受体又可以作为电子的供体,因此帮助了电荷在Si和目标分子之间的转移,这将为探索其它类似催化剂起到一定的帮助作用.     

Energy level shifts of CO chemisorbed and condensed on RH(111)

Energy level shifts of CO in different phases, gas, solid and chemisorbed on Rh(111) are compared. Between gaseous and solid CO a shift of the 4σ and 5σ derived molecular orbitals of about 2.7 eV to lower binding energies due to polarization is observed. A larger 1π – 4σ separation of the CO molecules condensed and chemisorbed on Rh(111) is observed with respect to the gas phase. A comparison of the binding energies of the three molecular orbitals in the different phases allows to estimate the bonding shift of the 5σ level to 2.7 eV.     

Linear carbon dioxide in the high-pressure high-temperature crystalline phase IV

High-temperature IR absorption spectra of solid CO2 in phases II and IV were measured in a resistive heated diamond anvil cell up to 30 GPa. The spectral structures of the bending mode, observed in high quality thin crystalline samples, and of the IR lattice phonons, measured for the first time between 80 and 640 K, are discussed using group theory arguments. According to this analysis the claimed bent molecular geometry of CO2 in phase IV can be unambiguously ruled out. Furthermore, the structures of both phases II and IV have been identified, among those so far proposed, as orthorhombic.     

Structural transformations and phase stabilization in Na2S04-Na2C03 system

The phase diagram of the system Na2S04-Na2C03 has been determined from room temperature upto liquidus. At low temperature the system shows partial miscibility and the formation of a compound, burkeite. At high temperature, the whole system shows complete miscibility and crystalizes in hexagonal system, with P63/m mc structure. This high temperature phase is quenched from the melt at room temperature, and shows: 1. Shortening of the hexagonal c-axis in the mixed series as a result of substitutions of tetrahedron complex with plane group. 2. Heat treatment of single crystals of intermediate phase of Na2S04 with Cmcm structure shows topotaxial phase change to high phases. 3. Na2CO3 rich region show satellite reflections, which vanish with rise of temperature. 4. Quenched high phase is metastable and reverts to low phases after sometime.     

Coadsorption of water and CO molecules on Ru(0 0 1) at high CO coverages: comparisons with a Ru(0 0 1) electrode surface

The coadsorption of carbon monoxide (CO) and water molecules on a Ru(0 0 1) surface has been studied by infrared spectroscopy, LEED and STM. At high CO coverage phases, a 2×2-(2CO+D₂O) structure was observed on both UHV and electrode surfaces. Electrode potential dependent structures from CO and water adlayers on an electrode surface were reproduced on a UHV surface by controlling molecular orientations of the first layer and second over-layer water molecules. At lower CO coverages, a CO band center showed coverage dependent shift down to 1444 cm⁻¹ due to an electron transfer from a lone pair of a water molecule to CO 2π^*.     

Coexistence of Charge Order and Antiferromagnetic Order in an Extended Periodic Anderson Model

The competition between the RKKY interaction and the Kondo effect leads to a magnetic phase transition,which occurs ubiquitously in heavy fermion materials.However,there are more and more experimental evidences indicating that the valence fluctuation plays an essential role in the Ce-and Y-based compounds.We study an extended periodic Anderson model(EPAM) which includes the onsite Coulomb repulsion Ucf between the localized electrons and conduction electrons.By employing the density matrix embed...     

Separating the vibrationally resolved Auger decay channels for a CO core hole state

The K-VV Auger spectrum of carbon monoxide (CO) excited by C 1s photoionization has been investigated with a novel electron-electron coincidence setup. The energy resolution is sufficiently high to resolve the vibrational energy levels of the core-ionized intermediate state and of most dicationic final states in the two-dimensional electron energy map. We demonstrate how the influence of vibrational states on a molecular Auger spectrum can be accessed experimentally without the constraint of averaging over all intermediate state energies.     

The oxidation of CO on pt(100): Mechanism and structure

Using dynamic LEED measurements of spot intensities and profiles, together with thermal desorption data, we have investigated the oxidation of CO on Pt(100)?(1 × 1). At T = 355 K, either CO or O was preadsorbed and reacted off with the other species. Results from both titration sequences point to the following conclusions: Titration of preadsorbed oxygen with CO_g leads to rapid reaction, with a reaction probability of unity for each chemisorbed CO. Adsorbed CO does not accumulate on the surface until θ_o ? 0.05, i.e. an intermediate, rather clean (1 × 1) Pt surface is obtained. Further evidence for this clean intermediate is provided by the fact that characteristics of the diffraction spots of the c(2 × 2) of CO develop identically during this reaction sequence and during adsorption of CO on a clean (1 × 1) Pt surface. In the reverse case, titration of preadsorbed CO with O_2,g, the reaction rate is slower than the oxygen adsorption rate, leading to a pressure-dependent development of coexisting O_ad and CO_ad domains, which we observe directly with LEED. The stable phases coexisting are the c(2 × 2) of CO and the oxygen-related (3 × 1). Thermal desorption peak shapes, together with LEED observations, indicate that the CO in this case is held in c(2 × 2) islands by a matrix of surrounding oxygen atoms. In no case do mixed structures form, nor is an existing structure compressed by subsequent adsorption of the second species. Starting from a Langmuir-Hinshelwood mechanism, the differences between the two reaction sequences are discussed in terms of different activation barriers for reaction and different sticking coefficients of the adsorbing species. Special attention is given to the mobilities of the adsorbed reactants.     

Universal aspects of coulomb-frustrated phase separation

We study the consequences of Coulomb interactions on a system undergoing a putative first order phase transition. In two dimensions (2D), near the critical density, the system is universally unstable to the formation of new intermediate phases, which we call "electronic microemulsion phases," which consist of an intermediate scale mixture of regions of the two competing phases. A corollary is that there can be no direct transition as a function of density from a 2D Wigner crystal to a uniform electron liquid. In 3D, if the strength of the Coulomb interactions exceeds a critical value, no phase separation occurs, while for the weaker Coulomb strength electronic microemulsions are inevitable. This tendency is considerably more pronounced in anisotropic (quasi-2D or quasi-1D) systems, where a devil's staircase of transitions is possible.     

高温下黑索金（RDX）热分解动力学模拟

应用分子动力学模拟方法研究了黑索金(RDX)在纯高温下的分解机理, 研究结果表明RDX初始分解机理主要为N-N键的断裂形成NO2分子, 然后发生H原子转移反应形成H2O, HONO, HO和NO分子; 通过对RDX热分解反应物和生成物的研究结果表明N2和H2O分子是RDX分解过程中最稳定的生成物, NO2, HNO3, NO, NO3和HONO分子为RDX热分解过程中的中间产物; 在高温4500K, CO, CO2和OH分子出现的频率逐渐提高, 表明这几种分子在高温下更容易形成.     

高温下黑索金（RDX）热分解动力学模拟

应用分子动力学模拟方法研究了黑索金(RDX)在纯高温下的分解机理, 研究结果表明RDX初始分解机理主要为N-N键的断裂形成NO2分子, 然后发生H原子转移反应形成H2O, HONO, HO和NO分子; 通过对RDX热分解反应物和生成物的研究结果表明N2和H2O分子是RDX分解过程中最稳定的生成物, NO2, HNO3, NO, NO3和HONO分子为RDX热分解过程中的中间产物; 在高温4500K, CO, CO2和OH分子出现的频率逐渐提高, 表明这几种分子在高温下更容易形成.     

Neutron studies of structural changes in amorphous C60 fullerite under temperature, pressure, and thermobaric effects

The structural behavior of amorphous fullerites obtained as a result of mechanical activation and thermal, baric, and thermobaric effects is studied via neutron diffraction. It is shown that the phase transition between the molecular crystal (fullerite) and atomic crystal (graphite) phases in the nanoscale state occurs through intermediate amorphous phases.     

Carbon monoxide dissociation on Rh nanopyramids

CO dissociation on rhomboidal faceted nanopyramids, produced on Rh(110) by fine-tuning of ion irradiation conditions, has been studied by high resolution core-level spectroscopy. We find that this morphology presents a large efficiency towards CO dissociation, a process which is inhibited on flat (110) terraces. We also measured the reactivity of nanostructures bound by different artificial step distributions identifying the sites responsible for the molecular bond disruption in the undercoordinated (n=6) edges running along the [11[over ]2] equivalent directions, with CO sitting in on-top configuration.     

铜基MOF的CO氧化机理

利用第一原理密度泛函理论,研究了CO在铜基MOF ( CuBTC )上氧化的反应机理。研究显示CO和O2 弱吸附在轮形Cu2构筑单元铜的顶位上,并且电子从O2和CO转移到Cu,通过两个机理(Eley-Rideal 机理和 Langmuir-Hinshelwood机理)的研究,揭示了CO在CuBTC的氧化是准Langmuir-Hinshelwood机理,先在铜上吸附的CO和氧气先越过1.8eV的能垒形成OOCO的中间体,然后分解成CO2,同时有活性氧吸附在Cu位,活性氧与第二个CO反应生成CO2。总的来说,研究有助于理解CO在铜基 MOFs的氧化。     

Staggered Phases in Diluted Systems with Continuous Spins

We consider systems with continuous spins and annealed dilution. We show that, as in the discrete case, such systems often undergo a phase transition, which is manifested in the appearance of a staggered intermediate phase. In particular, these phases appear in systems such as the massive Gaussian model where there is no phase transition in the undiluted system. Received: 2 January 1997 / Accepted: 1 February 1997     

Layer-scale optical chirality of liquid-crystalline phases

We present a model for the optical chirality of layered liquid-crystalline phases. The model demonstrates that uniform stacking of chiral layers can lead to significant collective optical rotation, even in the absence of a superlayer helix. We predict the optical rotation of the B2 phases of bent-core liquid crystals, which can have optical rotation as large as 1000 times the molecular optical activity.     

均相条件下NO与CO、NCO的反应机理研究

基于量子化学密度泛函理论研究了NO与CO、NCO在均相条件下的反应机理并进行了动力学和平衡常数的分析. CO与NO的均相反应存在两条反应路径：两者首先反应形成中间体CNO₂,CNO₂不易稳定存在,其继续与CO、NO反应分别生成NCO、N₂O. NCO的生成速率大于N₂O,但两条反应路径的反应速率常数都很小.与已发现的反应路径相比,反应中间体CNO₂可以降低均相条件下CO与NO的反应能垒,分析发现CNO₂中的N原子是易发生反应的活性位点. NCO与NO的反应同样存在两条路径,优势反应路径随温度升高而改变,但非优势路径对反应的贡献不能忽略,分析平衡常数可知N₂的存在对反应影响可以忽略,因此燃烧环境中NCO与NO的反应既生成N₂O和CO,也生成N₂和CO₂.