Alkali-induced enhancement of surface electronic polarizibility

From results of ab initio electronic structure calculations based on density functional theory for a set of prototype systems, we find alkali adsorbates to cause a dramatic enhancement of the electronic polarizability of the metal surface extending it several angstroms into the vacuum. This phenomenon is traceable to an unusual feature induced in the surface potential on alkali adsorption. The effect appears to be general, as we find it to be present on metals as varied as Pd and Cu, and helps explain the observed substantial decrease in the vibrational frequency of molecules when coadsorbed with alkalis on metal surfaces. Specifically, for two dissimilar molecules CO and O(2), we trace the softening of the frequencies of their stretching mode when coadsorbed with K on Pd(111) to the enhanced electronic polarizability.     

CO分子与碱金属原子在Fe(110)表面上的相互作用

本文介绍了CO分子分别与K原子或Na原子在Fe(110)表面上共吸附的研究。角分辨率紫外光电子能谱(ARUPS)的结果表明,碱金属原子在Fe(110)表面上的存在,紫外光电子能谱中出现了结合能低于通常CO分子1π能级的新峰。该峰位于费密能级以下6.3eV处,是C0在碱金属影响下电子结构改变的结果。该峰的出现对应着CO分子处于C—O键明显减弱的状态。偏振紫外光电子能谱的研究表明:6.3eV处的谱峰联系的电子轨道有一个对称平面和一个反对称平面,分别平行于<001>晶向和<110>晶向。CO分子轨道的对称性不因 关键词：     

The properties of K and coadsorbed CO + K on Ru (001): II. Electronic structure

The electronic properties of K and CO + K mixed layers on Ru(001) have been examined in detail with XPS, polarization and angle dependent UPS, and work function changes. The adsorption of K is accompanied by a gradual decrease of the K 2p binding energies and a normal work function behaviour which are discussed in detail. Adsorption of CO on K predosed surfaces also causes a K 2p binding energy decrease at all K coverages which can be understood as repulsion of substrate charge back into the K atom induced by CO orbitals overlapping with the substrate valence band. The complex change in work function caused by CO adsorption is explained by the combination of three effects, CO addition, charge exchange, and K displacement. All results in this and the first paper, in particular the additional peaks in the He I spectra and the HREELS results, are only compatible with the model of a sp²-rehybridized CO molecule in the vicinity of coadsorbed K.     

XPS and TPD investigation of CO adsorption on mixed Rh-V layers supported by gamma-alumina

Alumina-supported mixed bimetallic Rh-V thin films, with the overall thickness of 0.8 ML, were prepared under the ultrahigh vacuum (UHV) conditions and characterized with respect to their electronic and CO adsorption properties. X-ray photoelectron spectroscopy (XPS) was utilized to characterize electronic changes accompanying bimetallic Rh-V interaction and interaction between metal and polycrystalline γ-Al₂O₃ substrate. The chemisorption properties were probed by temperature-programmed desorption spectroscopy (TPD) of CO molecules. The electronic and chemisorption properties of the mixed layers were compared with pure Rh and V layers grown on the same γ-Al₂O₃ substrate and with a model bimetallic Rh-V system prepared by V deposition on a polycrystalline Rh foil. By varying the preparation conditions, we observed a strong dependence of the studied properties on the position of the V atoms. The presence of V atoms on the surface led to a fast deactivation, while vanadium presented under the surface resulted in a weakening of CO-metal surface bond, a change in the proportion of the adsorption side species, and an increase of CO dissociation.     

气体分子在类石墨烯材料负载单个金属原子表面的吸附特性

采用密度泛函理论方法研究了不同种类和数量的气体小分子在类石墨烯材料(graphenylene)衬底支撑的金属原子(M=Co, Mo和Pd, gra-M)表面的吸附特性,系统地分析了吸附不同数量的NO和CO分子的稳定构型,吸附能,电荷转移量以及引起的体系电子结构和磁性变化.研究结果表明:1) NO、CO气体小分子的稳定吸附位在金属原子顶位,吸附物与衬底间的电荷转移量表明负载不同的金属原子能够有效地调制类石墨烯材料的气敏特性;2)单个和两个气体分子吸附能够引起gra-M体系的自旋电荷密度分布发生变化,进而使得气体吸附体系表现出不同磁矩大小.     

Polarization effects on the surface chemistry of PbTiO3-supported Pt films

To demonstrate a new paradigm of dynamical control of surface structure and reactivity, we perform density functional theory calculations of the adsorption of several molecules and atoms to the surface of ultrathin Pt(100) films supported on ferroelectric PbTiO3. We show that reorienting the polarization direction of the substrate can dramatically change the chemisorption energies of CO, O, C, and N and alter the reaction pathways for dissociation of CO, O2, N2, and NO. We discuss the structural and electronic effects of a polarized substrate on the metal surface, and we suggest potential applications in tunable catalysis.     

Structural,electronic and catalytic performance of single-atom Fe anchored 3Si-doped graphene

By density functional theory (DFT) calculations, it is found that the single-atom Fe anchored three Si modified defective graphene (3Si-graphene-Fe) exhibits the high stability, and this system is semiconducting property and has non-magnetic moment. Besides the most stable configurations, electronic structures and magnetic properties of adsorbed species (O₂, CO, 2CO and CO/O₂) on 3Si-graphene-Fe systems are comparably discussed. The adsorption of O₂ is more stable than that of CO molecule and the coadsorption of 2CO and CO/O₂ has the larger adsorption energy than that of the isolated one. The adsorbed O₂, CO and CO/O₂ can induce the change in magnetic properties of 3Si-graphene-Fe system, and the coadsorbed CO/O₂ on system exhibits the metallic property. Among the reaction mechanisms, the CO oxidation reactions through Eley–Rideal (ER) reactions have lower energy barriers (<0.5?eV) than those of the Langmuir–Hinshelwood (LH) and new termolecular Eley–Rideal (TER) mechanisms, indicating that the ER reaction as starting step is an energetically favourable process. These results provide an important guidance on validating the catalytic activity of single atom on graphene-based materials.     

A REMPI study of the correlation of internal excitations and substrate-adsorbate coupling for CO molecules desorbed by electron impact

We compare vibrational, translational and rotational excitations of CO molecules desorbed by electron impact, and the yield of oxygen and carbon atoms from electron-induced fragmentation of CO molecules for: (1) CO monolayers on bare transition metals [Ru(001) and Pt(111)]; (2) CO monolayers coadsorbed with well-ordered oxygen atoms; (3) weakly bound CO monolayers on epitaxially grown silver films; and (4) CO monolayers decoupled from the metallic substrate by mono-atomic xenon spacer layers. For all but the last system, we find CO molecules which are vibrationally extremely hot. This is explained by the excitation of strongly antibonding multi-electron states which are quenched in the vicinity of the metal surface before enough translational energy is acquired by the nuclei to complete dissociation. For CO/Xe/Ag(111), vibrationally hot CO molecules are missing among the desorbing particles, whereas strong fragment signals persist. Because of the isolating Xe layer, the substrate-adsorbate coupling is too weak to terminate the dissociation reaction which is induced by the electron impact before the rupture of the molecular bond.     

Theoretical study on the catalytic properties of single-atom catalyst stabilised on silicon-doped graphene sheets

ABSTRACT

The stable configurations, electronic structures and catalytic activities of single-atom metal catalyst anchored silicon-doped graphene sheets (3Si-graphene-M, M?=?Ni and Pd) are investigated by using density functional theory calculations. Firstly, the adsorption stability and electronic property of different gas reactants (O₂, CO, 2CO, CO/O₂) on 3Si-graphene-M substrates are comparably analysed. It is found that the coadsorption of O₂/CO or 2CO molecules is more stable than that of the isolated O₂ or CO molecule. Meanwhile, the adsorbed species on 3Si-graphene-Ni sheet are more stable than those on the 3Si-graphene-Pd sheet. Secondly, the possible CO oxidation reactions on the 3Si-graphene-M are investigated through Eley–Rideal (ER), Langmuir–Hinshelwood (LH) and new termolecular Eley–Rideal (TER) mechanisms. Compared with the LH and TER mechanisms, the interaction between 2CO and O₂ molecules (O₂?+?CO → CO₃, CO₃?+?CO → 2CO₂) through ER reactions (< 0.2?eV) are an energetically more favourable. These results provide important reference for understanding the catalytic mechanism for CO oxidation on graphene-based catalyst.     

Mott insulator-superfluid phase transition in p-band triangle optical lattices with on-site rotation

In order to exploit the potential applications of graphene as gas sensors, the adsorptions of a series of small gas molecules (such as CO, O₂, NO₂ and H₂O) on pristine graphene (PG) and Si-doped graphene (SiG) have been investigated by ab initio calculations. Our results indicate that the electronic properties of PG are sensitive to O₂ and NO₂ molecules, but not changed much by the adsorption of CO and H₂O molecules. Compared with PG, SiG is much more reactive in the adsorption of CO, O₂, NO₂ and H₂O. The strong interactions between SiG and the adsorbed molecules induce dramatic changes to the electronic properties of SiG. Therefore, we suggest that SiG could be a good gas sensor for CO, O₂, NO₂ and H₂O.     

CO and O coadsorption on Pt3Sn studied by DFT: Changes in the adsorptive properties of the surface with alloying and coverage

Adsorption of CO and coadsorption of O and CO on Pt₃Sn(1 1 1) was studied using periodic DFT calculations. Calculations were performed on Pt(1 1 1) by using the same set of parameters and their results were used as reference basis. The calculations showed that the most stable configuration with the minimum energy for coadsorption of CO and O is CO adsorbed atop Pt and O adsorbed on fcc Pt2Sn hollow site and that the decrease in the adsorption strength of the system at a total surface coverage of 0.5 ML is by 0.063 eV as a result of coadsorption, with respect to the adsorption of one species individually. Results show that the interaction between the adsorbed CO and O is short range on PtSn alloy, contrary to that on pure Pt, and this is mainly related to stronger Sn–O bonds compared to Pt–O bonds which eventually reduce the surface strain at the coadsorption structure. There is a pronounced effect of total surface concentration on the adsorption energy of coadsorbed species; the adsorption strength is not directly proportional to the surface coverage but is also related to the distribution of the coadsorbed species on the surface.     

Structure Sensitive Reaction Channels of Molecular Hydrogen on Silicon Surfaces

The ability of the Si(001) surface to adsorb H2 molecules dissociatively increases by orders of magnitude when appropriate surface dangling bonds are terminated by H atoms. Through molecular beam techniques the energy dependent sticking probability at different adsorption sites on H-precovered and stepped surfaces is measured to obtain information about the barriers to adsorption, which decrease systematically with an increase in coadsorbed H atoms. With the help of density functional calculations for interdimer adsorption pathways, this effect is traced back to the electronic structure of the different adsorption sites and its interplay with local lattice distortions.     

用Xα-DV方法研究CO,NO在Ⅷ族过渡金属表面的化学吸附(Ⅱ)——NO分子在Pd(111)表面的化学吸附

本文用X_α-DV方法计算了NO在Pd(111)表面化学吸附问题。得到了它的电子结构,包括分子丛轨道能量本征值谱、态密度、电荷转移等等结果。在计算中特别考虑了NO之间的相互作用,所得总态密度与实验UPS十分相符,从而支持了LEED所示的几何结构,决定了NO的吸附高度为1.27?,并得知吸附于Pd表面的NO分子之间的相互作用十分重要。从理论上探讨了NO分子在Pd表面吸附时的活化作用。计算了NO分子各个轨道上的占有数,发现其电荷转移情况与CO在过渡金属表面吸附的情况相似。另外,还发现NO的吸附对Pd的价电子能带无重大影响。 关键词：     

Platinum and palladium as substrates for surface enhanced Raman spectroscopy

Surface enhanced Raman scattering (SERS) has been observed from the electrogenerated I₂ and I^-₃ coadsorbed on Pt and Pd electrodes. Theoretical models on the SERS process that emphasize the important role of the optical properties of the metal substrate cannot be used to explain this observation. The electronic interaction between the adsorbate and the substrate is believed to be the most important mechanism for the observed SERS.     

CO adsorption on alkali-metal covered Ni(100)

The effect of preadsorbed alkali metal atoms Na, K and Cs on CO adsorption on Ni(100) has been studied using Auger spectroscopy and thermal desorption. It was found that the presence of alkali metals causes an appearance of several more tightly bound states in the CO thermal desorption spectra. The observed difference in carbon and oxygen Auger peak line shape on a bare and alkali modified Ni(100) is indicative that the presence of alkali adatoms induces CO decomposition on the Ni(100) surface. The fraction of dissociated CO increases with the amount of alkali adatoms present. At the same overlayer coverage the dissociation probability increases in the sequence Na, K, Cs. A comparison of the strength of the promoting effect on CO dissociation with the changes in the surface electron density in the presence of alkali adatoms has shown that at low overlayer coverages the electronic factor plays a major role in explaining the action of the surface modificators.     

Ab initio molecular orbital calculations of transition metal complexes

All electron ab initio SCF-MO calculations in a better-than-minimal basis of the electronic structures of Mn(CO)₅H, Mn(CO)₅CH₃, Mn(CO)₅Cl and Mn(CO)₅CN are reported. The nature of the bonding of the CO groups, and of the other ligand to the central metal atom is discussed, together with the effect of the substituent on the electronic structure of the carbonyl ligands. The calculated wavefunctions are used to discuss the low energy photoelectron spectra, and other experimental data on these molecules.     

Density functional theory study on the adsorption of alkali metal ions with pristine and defected graphene sheet

The graphene-based materials along with the adsorption of alkali metal ions are suitable for energy conversion and storage applications. Hence in the present work, we have investigated the structural and electronic properties of pristine and defected graphene sheet upon the adsorption of alkali metal ions (Li⁺, Na⁺, and K⁺) using density functional theory (DFT) calculations. The presence of vacancies or vacancy defects enhances the adsorption of alkali ions than the pristine sheet. From the obtained results, it is found that the adsorption energy of Li⁺ on the vacancies defected graphene sheet is higher (3.05?eV) than the pristine (2.41?eV) and Stone–Wales (2.50?eV) defected sheets. Moreover, the pore radius of the pristine and defected graphene sheets are less affected by metal ions adsorption. The increase in energy gap upon the adsorption of metal ions is found to be high in the vacancy defected graphene than that of other sheets. The metal ions adsorption in the defective vacancy sheets has high charge transfer from metal ions to the graphene sheet. The bonding characteristic between the metal ions and graphene sheet are analysed using QTAIM analysis. The influence of alkali ions on the electronic properties of the graphene sheet is examined from the Total Density of States (TDOS) and Partial Density of States (PDOS).     

The influence of potassium and the role of coadsorbed oxygen on the chemisorptive properties of Pt(100)

The adsorption of K on Pt(100) has been followed by thermal desorption spectroscopy (TDS) and Auger electron spectroscopy (AES); carbon monoxide was used as a probe for the modification of the chemical properties of K promoted surfaces. The role of subsequent adsorption of oxygen on the K modified surfaces has also been measured. For low potassium coverage (θ_K = 0 to 0.35), the mass-28 TDS peak temperature of adsorbed CO increases continuously with the K coverage, indicating an increase of the adsorption energy of CO which has been explained by a substantial charge donation from K into the $\text{2π}{}^1$ orbitals of CO via long range interactions through the platinum substrate. No oxygen uptake was detected after oxygen exposure at room temperature. For high potassium content (θ_K = 0.45 to 1), the mass-28 TDS peak temperature of coadsorbed CO is very narrow and remains constant at 680 K. We propose the formation of a COKPt surface complex which decomposes at 680 K, since K desorption is detected concomitantly to CO. On such K covered surfaces, the oxygen uptake is promoted, and it cancels the modifications of the surface properties induced by potassium.     

Structure and electronic factors in benzene coordination to Cr(CO)3 and to cluster models of Ni,Pt, and Ag (111) surfaces

Bonding of benzene to a chromium tricarbonyl fragment and to cluster models of silver, nickel, and platinum (111) surfaces is found by means of molecular orbital calculations to be dominated by a benzene donation bond involving its π (e_1g) orbitals and metal d orbitals. Three-fold hollow sites on the clusters are calculated to be most stable for benzene coordination, a conclusion reached in a number of experimental studies of benzene on metal surfaces. On the Ag, Ni, and pt clusters, the benzene CH bonds are found to bend away from the surface by ?2°, 8° and 19°, respectively, a result of carbon atom hybridization to maximize overlap with metal orbitals. For benzene chromium tricarbonyl, the CH bonds are calculated to bend 3° toward the metal, compared to a 1.7° bend reported in a diffraction study. The direction and magnitude of the CH bending are shown to depend on the metal d orbital occupancy (an electronic factor) and the proximity of metal atoms in the adsorption site (a structure factor). Small Kekulé distortions are calculated for the chromium complex and for the C_3v sites on Pt(111). Finally, recent experimental studies showing a decrease in benzene adsorption energy when potassium is coadsorbed on Pt(111) may be understood to result from decreased π donation which accompanies the shift up of the metal d band with cathodic charging.     

The coadsorption of CO and H2 on Fe(100)

The coadsorption of CO and hydrogen on an Fe(100) surface was studied by temperature programmed desorption and X-ray photoelectron spectroscopy. It was found that CO adsorption blocked the subsequent dissociative adsorption of H₂, although it did not seem to affect the hydrogen binding energy. Preadsorption of hydrogen was observed to reduce the binding energy of CO subsequently adsorbed and to inhibit the dissociation of CO. A new surface species was identified in a coadsorbed layer of CO and hydrogen. This species was evidenced by the formation of a desorption peak for H₂ at 475 K when CO was adsorbed subsequent to H₂ adsorption.