共查询到20条相似文献,搜索用时 605 毫秒
1.
A. Forni G. Wiesenekker E. J. Baerends G. F. Tantardini 《International journal of quantum chemistry》1994,52(4):1067-1080
Ab initio band-structure calculations within a density functional formalism were performed to compute the binding energy curves of atomic hydrogen with the high-symmetry adsorption sites of the (111) surface of copper. For a two-layer slab of Cu atoms and H coverage equal to 0.25, the binding energies are 2.25, 3.12, and 3.24 eV, for on-top, bridge, and threefold sites, so that the chemisorption of H2 on Cu(111) is exothermic for threefold and bridge sites, but endothermic for on-top sites. Starting from these results, an LEPS potential for the interaction of H2 with the Cu(111) surface was built. In this model potential, the most favored approaches correspond to a H2 molecule parallel to the Cu surface, and for them, the activation barrier is located at the corner between the entrance and the exit channels of the reaction, and its lowest value is 0.6 eV. The LEPS potential was used in quasi-classical trajectories calculations to simulate the adsorption of a beam of H2 molecules on Cu(111). The results show that (a) when H2 is in the ground vibrational state the dissociative adsorption probability Pa increases from 0 to .90 along a roughly sigmoidal curve by increasing the collision kinetic energy from 0.4 to 1.3 eV, and (b) the vibrational energy can be as effective as the translational one in promoting dissociative chemisorption, in agreement with the experimental results. © 1994 John Wiley & Sons, Inc. 相似文献
2.
Xinli Leng Yan Lu Zhongping Wang Wei Li Xiaoqing Liu Li Wang 《Surface and interface analysis : SIA》2016,48(4):237-242
The metalation behaviors of 5,15‐diphenylporphyrin (2H‐DPP) on Pd(111) and Cu/Pd(111) have been investigated using scanning tunneling microscopy and density functional calculations. We show that 2H‐DPP molecules deposited on Pd(111) surface form Pd‐DPP with a proportion of about 75% already at room temperature (RT). This is in contrast to non‐metalation adsorption of 2H‐DPP on Cu–Pd alloy at RT. Annealing to 323 K facilitates the metalation of 2H‐DPP on Cu–Pd alloy island. The comparison of the results indicates that the metalation of 2H‐DPP calls for both enough surface free energy of approaching N? H bond and enough reactivity of breaking N? H bond. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
3.
Static investigation of adsorption and hetero‐diffusion of copper,silver, and gold adatoms on the (111) surface 下载免费PDF全文
A. Kotri E. El koraychy M. Mazroui Y. Boughaleb 《Surface and interface analysis : SIA》2017,49(8):705-711
In this work, we have used the static molecular simulations combined with an interatomic potential derived from the embedded‐atom method to study the adsorption and hetero‐diffusion on the (111) surface of Cu, Ag, and Au adatoms by using LAMMPS code. The investigation is performed for six heterogeneous systems such as Ag/Au(111), Ag/Cu(111), Au/Ag(111), Au/Cu(111), Cu/Ag(111), and Cu/Au(111). First, we have investigated the relaxation trends and the bond lengths of the atoms in the systems. The calculation results show that, the top layer spacing between the first and second layers of the Au(111), Ag(111), and Cu(111) substrates is contracted. This contraction is found to be more important in the Au(111) substrate. On the other hand, the strong reduction of the binding length is found in Au/Cu(111) for the different adsorption sites. In addition, the binding, adsorption, and static activation energies for all studied systems were examined. The results indicated that the binding and adsorption energies reached their maximum values in the Au/Cu(111) and Au/Ag(111) systems, respectively. Moreover, the static activation barriers for hopping diffusion on the (111) surfaces are found to be low compared with those found in the (100) and (110) surfaces. Therefore, our calculations showed that the difference in energy between the hcp and fcc sites on the (111) surfaces is very small. Copyright © 2017 John Wiley & Sons, Ltd. 相似文献
4.
Conformation Diversity of a Fused‐Ring Pyrazine Derivative on Au(111) and Highly Ordered Pyrolytic Graphite 下载免费PDF全文
Hui‐Juan Yan Nadja Sändig Haifeng Wang Dong Wang Francesco Zerbetto Xiaowei Zhan Li‐Jun Wan 《化学:亚洲杂志》2015,10(6):1311-1317
Heterocyclic aromatic compounds have attracted considerable attention because of their high carrier mobility that can be exploited in organic field‐effect transistors. This contribution presents a comparative study of the packing structure of 3,6‐didodecyl‐12‐(3,6‐didodecylphenanthro[9,10‐b]phenazin‐13‐yl)phenanthro[9,10‐b]phenazine (DP), an N‐heterocyclic aromatic compound, on Au(111) and highly ordered pyrolytic graphite (HOPG). High‐resolution scanning tunneling microscopy (STM) combined with atomistic simulations provide a picture of the interface of this organic semiconductor on an electrode that can have an impact on the field‐effect transistor (FET) performance. DP molecules adsorb with different conformational isomers (R/S: trans isomers; C: cis isomer) on HOPG and Au(111) substrates. All three isomers are found in the long‐range disordered lamella domains on Au(111). In contrast, only the R/S trans isomers self‐assemble into stable chiral domains on the HOPG surface. The substrate‐dependent adsorption configuration selectivity is supported by theoretical calculations. The van der Waals interaction between the molecules and the substrate dominates the adsorption binding energy of the DP molecules on the solid surface. The results provide molecular evidence of the interface structures of organic semiconductors on electrode surfaces. 相似文献
5.
Scanning tunneling microscopy (STM) combined with density functional theory (DFT) calculations were applied in studying the anisotropic adsorption and condensation of tert‐butylamine (t‐BA) molecules in the vicinity of the steps on the Cu(111) surface. The preferential adsorption at the upper step edges and uneven distribution of t‐BA in the vicinity of the steps illustrate the asymmetric electronic structure of the surface steps. Our observation demonstrates that the adsorption and diffusion of a polar molecule would be significantly mediated by steps on metal surfaces due to the molecule–step interaction and the intermolecular interactions. 相似文献
6.
采用基于密度泛函理论的第一性原理方法和平板模型研究了CH3SH分子在Cu(111)表面的吸附反应.系统地计算了S原子在不同位置以不同方式吸附的一系列构型, 第一次得到未解离的CH3SH分子在Cu(111)表面顶位上的稳定吸附构型,该构型吸附属于弱的化学吸附, 吸附能为0.39 eV. 计算同时发现在热力学上解离结构比未解离结构更加稳定. 解离的CH3S吸附在桥位和中空位之间, 吸附能为0.75-0.77 eV. 计算分析了未解离吸附到解离吸附的两条反应路径, 最小能量路径的能垒为0.57 eV. 计算结果还表明S―H键断裂后的H原子并不是以H2分子的形式从表面解吸附而是以与表面成键的形式存在. 通过比较S原子在独立的CH3SH分子和吸附状态下的局域态密度, 发现S―H键断裂后S原子和表面的键合强于未断裂时S原子和表面的键合. 相似文献
7.
Eva Marie Freiberger Dr. Florian Späth Dr. Udo Bauer Dr. Fabian Düll Dr. Philipp Bachmann Johann Steinhauer Felix Hemauer Natalie J. Waleska Valentin Schwaab Prof. Dr. Hans-Peter Steinrück Dr. Christian Papp 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(52):13172-13180
We present detailed studies on the covalent adsorption of molecular oxygen and atomic hydrogen on the hexagonal boron nitride (h-BN) nanomesh on Rh(111). The functionalization of this two-dimensional (2D) material was investigated under ultra-high vacuum conditions using synchrotron radiation-based in situ high-resolution X-ray photoelectron spectroscopy, temperature-programmed X-ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy. We are able to provide a deep insight into the adsorption behavior and thermal stability of oxygen and hydrogen on h-BN/Rh(111). Oxygen functionalization was achieved via a supersonic molecular beam while hydrogen functionalization was realized using an atomic hydrogen source. Adsorption of the respective species was observed to occur selectively in the pores of h-BN leading to spatially defined modification of the 2D layer. The adsorption of the observed molecular oxygen species was found to be an activated process that requires high-energy oxygen molecules. Upon heating to 700 K, oxygen functionalization was observed to be almost reversible except for small amounts of boron oxides evolving due to the reaction of oxygen with the 2D material. Hydrogen functionalization of h-BN/Rh(111) was fully reversed upon heating to about 640 K. 相似文献
8.
The adsorption and decomposition of HMX and CL‐20 molecules on the Al(111) surface were investigated by the generalized gradient approximation of density functional theory. The calculations employed a supercell (6 × 6 × 3) slab model and three‐dimensional periodic boundary conditions. The strong attractive forces between HMX (or CL‐20) molecule and Al atoms induce the breaking of N‐O and N‐N bonds in nitro group. Subsequently, the dissociated oxygen atoms, NO2 groups, and radical fragments of HMX or CL‐20 oxidize the Al surface. The largest adsorption energy is ?1792.7 kJ/mol in B1, where CL‐20 decomposes into four O atoms and a CL‐20 fragment. With the number of the radical species in adsorption configurations increases, the corresponding adsorption energy increases greatly. We also investigated the decomposition mechanism of HMX and CL‐20 molecules on the Al(111) surface. The activation energies (E a) for the dissociations A2, A3, B1, and B6 are 31.2, 47.9, 75.5, and 75.9 kJ/mol, respectively. Although CL‐20 is more sensitive than HMX in its gaseous state, the E a of CL‐20 is higher than that of HMX when they adsorb and decompose on the Al(111) surface, which indicates that the HMX is even easier to decompose on Al(111) surface as compared with CL‐20. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
9.
Iva Matolínová Viktor Johánek Josef Mysliveček Kevin C. Prince Tomáš Skála Michal Škoda Nataliya Tsud Mykhailo Vorokhta Vladimír Matolín 《Surface and interface analysis : SIA》2011,43(10):1325-1331
Methanol adsorption on ion‐sputtered Pt(111) surface exhibiting high concentration of vacancy islands and on (2 × 1)Pt(110) single crystal were investigated by means of photoelectron spectroscopy (PES) and thermal desorption spectroscopy. The measurements showed that methanol adsorbed at low temperature on sputtered Pt(111) and on (2 × 1)Pt(110) surfaces decomposed upon heating. The PES data of methanol adsorption were compared to the data of CO adsorbed on the same Pt single crystal surfaces. In the case of the sputtered Pt(111) surface, the dehydrogenation of HxCO intermediates is followed by the CO bond breakage. On the (2 × 1)Pt(110) surface, carbon monoxide, as product of methanol decomposition, desorbed molecularly without appearance of any traces of atomic carbon. By comparing both platinum surfaces we conclude that methanol decomposition occurs at higher temperature on sputtered Pt(111) than on (2 × 1)Pt(110). Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
10.
Rao BV Kwon KY Zhang J Liu A Bartels L 《Langmuir : the ACS journal of surfaces and colloids》2004,20(11):4406-4412
We present a low-temperature scanning tunneling microscopy study of increasing coverages of 2,5-dichlorothiophenol, an asymmetrically halo-substituted aromatic thiol, on Cu(111). At low coverage, deprotonation of the thiol occurs spontaneously upon adsorption at 80 K. Albeit the low deposition temperature, we find the formation of adsorbate islands at low coverage, which coalesce into a well-ordered film of horizontally adsorbed molecules at increasing coverage. This behavior indicates (i) significant mobility of the thiols on Cu(111) even at low temperatures and (ii) attractive adsorbate-adsorbate interactions. At higher coverages intermolecular interactions prevent long-range diffusion of adsorbates and thermal activation of the S-H bond becomes necessary. A close analysis of the molecular films reveals chiral recognition between neighboring molecules, which leads to the formation of enantiopure areas on the surface. Upright orientation of individual molecules starts at the boundaries between such phases and can be induced by scanning tunneling microscopy. 相似文献
11.
The adsorption of (R)- and (S)-2-phenylpropionamide (PPA, C(9)H(11)ON) molecules on a Cu(111) surface has been investigated using the density functional method with supercell models. The adsorption orientations of both (R)- and (S)-PPA molecules on the surface are the same: the phenyl rings are approximately parallel to the Cu(111) surface and positioned in the hollow sites, the amino and methyl groups occupy two-bridge sites, and the carbonyl occupies the top site. After the adsorption, the bond lengths in the two enantiomers are almost unchanged, but the changes for two dihedral angles show differences, especially for (R)-PPA molecule. The first angles between the (N,C9,C7) plane and the (C9,C7,C6) plane are 19.4 and 0.7 degrees for (R)- and (S)-PPA molecules, respectively, and the second angles between the (C8,C7,C6) plane and the (C7,C6,C5) plane are 74.8 and 0.4 degrees for (R)- and (S)-PPA molecules, respectively. The adsorption energies of (R)- and (S)-PPA molecules are calculated to be -34 and -26 kJ mol(-1), respectively. The simulated scanning tunneling microscopy (STM) images of (R)- and (S)-PPA molecules on the Cu(111) surface display different features and are coincident with the experimental ones. The interaction between the adsorption molecule and the metal surface is found to be responsible for the discrimination of (R)- and (S)-PPA molecules on the surface. 相似文献
12.
CH(x) (x=1-3) adsorptions on clean and CO precovered Rh(111) surfaces were studied by density functional theory calculations. It is found that CH(x) (x=1-3) radicals prefer threefold hollow sites on Rh(111) surfaces, and the bond strength between CH(x) and Rh(111) follows the order of CH(3)相似文献
13.
Water adsorption on Pt(111) surfaces treated with oxygen or hydrogen chloride at 20 K has been studied by Fourier transform infrared spectroscopy and scanning tunneling microscopy. Water molecules chemisorb predominantly on the sites of the electronegative additives (O or Cl-), forming hydrogen bonds of O-HO or O-HCl-. On a Pt(111)-2×2-O surface, water adsorption produces species (O(D2O)), monomeric water (D2O), (O(D2O)2) and ring tetramer-like cluster (O(D2O)3) on a Pt(111) surface. On a Pt(111)-3×3-Cl- (θ=0.44) surface, water adsorption gives rise to a Pt(111)-(4×2)-(H3O++Cl-) co-adsorption structure to form a hydrogen-bonding network between Cl- and H3O+ ions. 相似文献
14.
15.
16.
ZHANG Junjie WANG Can DUAN Ruomeng PENG Chencheng YANG Biao CAO Nan ZHANG Haiming CHI Lifeng 《高等学校化学研究》2020,36(4):685-689
The derivatives of aromatic cores bearing alkyl chains with different lengths are of potential interest in on-surface chemistry, and thus have been widely investigated both at liquid-solid interfaces and in vacuum. Here, we report on the structural evaluation of self-assembled 1,3,5-tri(4-dodecylphenyl)benzene(TDPB) molecules with increased molecular coverages on both Au(111) and Cu(111) surfaces. As observed on Au(111), rhombic and herringbone structures emerge successively depending on surface coverage. In the case of Cu(111), the same process of phase conversion is also observed, but with two distinct structures. In comparison, the self-assembled structures on Au(111) surface are packed more densely than that on Cu(111) surface under the same preparation conditions. This may fundamentally result from the higher adsorption energy of TDPB molecules on Cu(111), restricting their adjustment to optimize a thermodynamically favorable molecular packing. 相似文献
17.
Coverage‐ and Temperature‐Dependent Metalation and Dehydrogenation of Tetraphenylporphyrin on Cu(111) 下载免费PDF全文
Michael Röckert Matthias Franke Quratulain Tariq Stefanie Ditze Michael Stark Patrick Uffinger Daniel Wechsler Upendra Singh Dr. Jie Xiao Dr. Hubertus Marbach Prof. Dr. Hans‐Peter Steinrück Dr. Ole Lytken 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(29):8948-8953
Using temperature‐programmed desorption, supported by X‐ray photoelectron spectroscopy and scanning tunneling microscopy, a comprehensive overview of the main reactions of 5,10,15,20‐tetraphenyl‐21H,23H‐porphyrin (2HTPP) on Cu(111) as a function of coverage and temperature is obtained. Three reactions were identified: metalation with Cu substrate atoms, stepwise partial dehydrogenation, and finally complete dehydrogenation. At low coverage the reactions are independent of coverage, but at higher coverage metalation becomes faster and partial dehydrogenation slower. This behavior is explained by a weaker interaction between the iminic nitrogen atoms and the Cu(111) surface in the high‐coverage checkerboard structure, leading to faster metalation, and the stabilizing effect of T‐type interactions in the CuTPP islands formed at high coverage after metalation, leading to slower dehydrogenation. Based on the amount of hydrogen released and the appearance in STM, a structure of the partially dehydrogenated molecule is suggested. 相似文献
18.
《无机化学与普通化学杂志》2018,644(8-9):415-423
In porous Prussian blue (PB) analogues, the partially naked central metal atoms found at the cavities surface are responsible for many of their physical properties, among them the adsorption potentials. In the as‐synthesized PB analogues, such metal sites stabilize water molecules inside the cavity through coordination bond formation. The filling of the cavity volume is completed with water molecules linked to the coordinated ones through hydrogen bonds formation. Vanadyl‐based PB analogue shows quite different features. The metal(V) at the cavities surface has saturated its coordination sphere with the O atom of the vanadyl ion (V=O). In this material, the V=O group preserves enough strong dipole moment to stabilize adsorbed species at the cavity through dipole–dipole and dipole–quadrupole interactions. This contribution reports the preparation, crystal structure and properties for (VO)3[M(CN)6]2 · nH2O (M = Fe, Co). According to the refined crystal structure, IR spectra and TG data, six water molecules remain stabilized inside the cavities through a strong dipole–dipole coupling with the vanadyl group. The cavity contains additional water molecules interacting through hydrogen bond bridges with the water molecules coupled to the V=O group. The vanadyl ion is free of hydrogen bonding interactions with the water molecules. The recorded adsorption isotherms for N2, CO2 and H2, three molecules with only quadrupole moment, reveal presence of relative strong adsorption forces due to dipole‐quadrupole interactions. 相似文献
19.
Davide Curcio Emil Sierda Monica Pozzo Luca Bignardi Luca Sbuelz Paolo Lacovig Silvano Lizzit Dario Alf Alessandro Baraldi 《Chemical science》2021,12(1):170
In this work, we characterize the adsorption of pentacene molecules on Ir(111) and their behaviour as a function of temperature. While room temperature adsorption preserves the molecular structure of the five benzene rings and the bonds between carbon and hydrogen atoms, we find that complete C–H molecular break up takes place between 450 K and 550 K, eventually resulting in the formation of small graphene islands at temperatures larger than 800 K. Most importantly a reversible temperature-induced dehydrogenation process is found when the system is annealed/cooled in a hydrogen atmosphere with a pressure higher than 5 × 10−7 mbar. This novel process could have interesting implications for the synthesis of larger acenes and for the manipulation of graphene nanoribbon properties.In this work, we characterise the adsorption of pentacene molecules on Ir(111) and their dissociation behaviour as a function of temperature. 相似文献
20.
Diao YX Han MJ Wan LJ Itaya K Uchida T Miyake H Yamakata A Osawa M 《Langmuir : the ACS journal of surfaces and colloids》2006,22(8):3640-3646
The adsorption of 4,4'-bipyridine (BiPy) on Cu(111) has been investigated in 0.1 M HClO4 by cyclic voltammetry, electrochemical scanning tunneling microscopy (STM), and surface-enhanced infrared adsorption spectroscopy (SEIRAS). Cyclic voltammetry showed the double layer region extending from -0.2 to 0.26 V and a pair of redox waves superposing on hydrogen evolution wave at more negative potentials. Diprotonated BiPy, BiPyH2(2+), is adsorbed flat on the Cu(111) (1 x 1) surface and forms a well-ordered monolayer with a (3 x 4) symmetry in the double-layer potential region. At more negative potential, BiPyH2(2+) is reduced to its monocation radical, BiPyH2(*+), and forms another well-ordered structure in which the radicals are stacked in molecular rows with a face-to-face self-dimer as the building unit. The SEIRA spectra of both BiPyH2(2+) and BiPyH2(*+) are dominated by gerade modes which should be IR-inactive for the centrosymmetric species. The breakdown of the selection rule of IR absorption is ascribed to the vibronic coupling associated with charge transfer between BiPyH2(2+) and the surface and between the radicals. 相似文献