Preparation and characterization of Cr(CO)(4)dpp (chromium tetracarbonyl 2,3-bis(2'-pyridyl)pyrazine) adsorbed on silver nanoparticles

A transition metal carbonyl species, Cr(CO)(4)dpp, has been successfully attached to bare silver nanoparticles prepared by laser ablation of a metal foil in ethanol. Transmission electron microscopy (TEM) images have shown that at least a portion of the silver nanoparticles have been capped by the chromium species, and ligand shells corresponding to Cr(CO)(4)dpp multilayer adsorption onto the silver nanoparticles of 30-50 nm diameter have been observed. The detection of the strongest Raman-active nu(CO) band of Cr(CO)(4)dpp at 2004 cm(-1) revealed that the species has been adsorbed without decomposition. The time-of-flight secondary ion mass spectrometry (TOF-SIMS) signals recorded of the chromium-capped silver nanoparticles were also consistent with the nondecomposition adsorption process. Density functional calculations have been used to reproduce the Raman spectrum using Ag(7)(+) as a model surface. A large binding energy of about 122 kJ/mol has also been computed between silver and nitrogen atoms thus lending support to Cr(CO)(4)dpp being chemisorbed onto the silver surface.     

密度泛函理论研究十二烷硫醇在Au(111)面上的吸附

采用第一性原理方法研究了十二烷硫醇(C₁₂H₂₅SH)分子在Au(111)面上未解离和解离吸附的结构、能量和吸附性质,在此基础上分析判断长链硫醇分子在Au(111)面吸附时S―H键的解离, 以及分子链长度对吸附结构和能量的影响. 计算了S原子在不同位置以不同方式吸附的系列构型, 结果表明在S―H键解离前和解离后,均存在两种可能的表面结构, 直立吸附构型和平铺吸附构型; 未解离的C₁₂H₂₅SH分子倾向于吸附在top位, 吸附能为0.35-0.38 eV; H原子解离后C₁₂H₂₅S基团倾向于吸附在bri-fcc位, 吸附能量为2.01-2.09 eV. 比较分析未解离吸附和解离吸附, 发现C₁₂H₂₅SH分子未解离吸附相较于解离吸附要稳定, 未解离吸附属于弱化学吸附.局域电子态密度和差分电荷密度分析进一步验证了S―H解离后S原子与表面之间成键的数目增加, 而且键合更强. 同时我们发现长链硫醇的吸附能量较短链硫醇的吸附能量略大, S原子与表面Au原子之间的距离略小.     

Interaction of Photoactive[Fe（CN）6]4^- with TiO2 Anatase（101） Surface： A Periodic Density Functional Theory Study

The plane-wave pseudopotential function method,based on density-functional theory,has been used to calculate the adsorption,electronic band structures,orbitals and optical absorption spectrum of [Fe(CN)6]4-on TiO2 anatase(101) surface. Our calculations reveal that the surface-modified anatase system has large adsorption energy and a much narrower band gap. [Fe(CN)6]4-adsorption on the (101) surface could lead to a large red shift of the anatase optical absorption threshold,which extends into a visible region significantly. The calculated results are in agreement with the experiment and other theoretical studies reasonably. It is very important for the understanding and further development of photovoltaic materials that are active under visible light.     

Infrared Spectra of Alkylphosphonic Acid Bound to Aluminium Surfaces

Summary: The infrared absorption (IR) spectrum of alkyl phosphonic acid adsorbed on the α-Al₂O₃ (0001) surface has been calculated by means of a density-functional based tight-binding method. Thereby mono-dentate, bi-dentate and tri-dentate bonding of the acid to the surface have been considered. In addition, experimentally obtained Fourier Transform Infrared Spectra (FTIR) of octadecylphosphonic acid (ODPA) on the natural surface of aluminium have been included. The absence of the PO band in the experimental surface spectrum and in the calculated spectrum of the tridentate adsorption complexes showed that adsorption of (alkyl)phosphonic acids on aluminium favours tridentate bonding, where the acid is bound to the surface via three symmetric P O Al bonds.     

Infrared spectroscopic studies of monothiol ligand adsorption on CdS nanocrystal films in aqueous solutions

Probing the surface chemistry of thiol ligand binding to cadmium chalcogenide nanocrystals is important to clarify factors involved in quantum dot stability and surface functionalization. Deposited CdS nanocrystal films have been used in this work as model quantum dot surfaces for ligand adsorption studies. The adsorption of mercaptoacetic acid, mercaptopropionic acid, and mercaptoethanol, from aqueous solution to CdS thin films, has been studied by in situ infrared spectroscopy. The absence of a S-H stretch absorption for the adsorbed species shows that adsorption occurs via the deprotonated thiol group, and the spectrum of the adsorbed carboxylic acid species closely resembles those of the solution ligands. Adsorption of mercaptoacetic acid and of mercaptopropionic acid resulted in pKa(COOH) decreases of 1.5 and 0.5, respectively. Significant changes in the spectrum of mercaptoethanol upon adsorption have been observed, but the present uncertainty in mercaptoethanol spectral interpretation does not provide structural inferences. Adsorption isotherms determined from the spectral data indicate strong thiol adsorption to CdS. The adsorption isotherms have been fitted to both Langmuir and Freundlich equations, with the latter providing a better fit. This may be attributed to a change in the probability of adsorption to vacant surface sites due to the increased CdS surface negative charge as the surface coverage increases.     

Coadsorption of CO and O(2) on selected gold clusters: evidence for efficient room-temperature CO(2) generation

Spurred by the recent demonstrations of the size- and support-dependent reactivity of supported gold clusters, here we present results on the coadsorption of CO and O(2) on selected anionic gold clusters, Au(N)(-), in the gas phase. O(2) adsorbs in a binary (0,1) fashion as a one-electron acceptor on the Au(N)()(-) clusters, with even-N clusters showing varying reactivity toward O(2) adsorption, while odd-N clusters show no evidence of reactivity. CO shows a highly size-dependent reactivity for Au(N)(-) sizes from N = 4 to 19, but no adsorption on the gold dimer or trimer. When the gold clusters are exposed to both reactants, either simultaneously or sequentially, interesting effects have been observed. While the same rules pertaining to individual O(2) or CO adsorption continue to apply, the preadsorption of one reactant on a cluster may lead to the increased reactivity of the cluster to the other reactant. Thus, the adsorbates are not competing for bonding sites (competitive coadsorption), but, instead, aid in the adsorption of one another (cooperative coadsorption). New peaks also arise in the mass spectrum of Au(6)(-) under CO and O(2) coadsorption conditions, which can be attributed to the loss of a CO(2) molecule (or molecules). By studying the relative amount of reaction, and relating it to the reaction time, it is found that the gas-phase Au(6) anion is capable of oxidizing CO at a rate 100 times that reported for commercial or model gold catalysts.     

A first-principles study of (R)- and (S)-PPA Molecules on Cu(111)

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.     

My voyage of discovery to proteins in flatland ...and beyond

The 9th-10th type III fibronectin domain pair (9-10FNIII) has found widespread use as a biomimetic surface for cell adhesion. However, the effect of mutations to 9-10FNIII on its surface adsorption characteristics have not been investigated. Here we address this issue using total internal reflection fluorescence (TIRF) and circular dichroism spectroscopy, comparing two conformationally stable 9-10FNIII mutants against the wild type. Desorption of the 9-10FNIII mutants from the silica surface was minimal in comparison to desorption of 9-10FNIII. The extent and rate of protein desorption from silica was empirically matched by loss of secondary structure upon adsorption, with only the spectrum for 9-10FNIII showing extensive loss of the beta-sandwich fold. For the proteins adsorbed to hydrophobic surfaces, only the CD spectra for the 9-10FNIII mutant constrained via an interdomain disulphide bridge showed similarity with the corresponding solution structure. Since the binding of 9-10FNIII to integrin alpha5beta1 is highly dependent on the relative spatial arrangement of the two domains, we suggest that the observed differences in cell adhesion and spreading on wild type 9-10FNIII and mutants may in part be attributed to the extent of protein desorption and unfolding at the surface.     

Experimental and theoretical surface enhanced Raman scattering study of 2-amino-4-methylbenzothiazole adsorbed on colloidal silver particles

The adsorption of 2-amino-4-methylbenzothiazole (2-AMBT) on colloidal silver particles has been investigated by a surface enhanced Raman scattering (SERS) study. The SERS spectra of the 2-AMBT molecule at varied adsorbate concentrations recorded in different time domains are compared with its Fourier transform infrared (FTIR) spectrum and normal Raman spectrum (NRS) in the bulk and in solution. The experimentally observed SERS spectra are compared with the theoretically modeled surface complexes using ab initio restricted Hatree-Fock (RHF) and density functional theory (DFT) calculations. The most favorable adsorptive sites of the 2-AMBT molecule have been estimated by natural population analysis (NPA) using the above-mentioned high level of theories. The enhancement of the in-plane modes together with the appearance of Ag-N stretching frequency at 215 cm(-1) indicates that the 2-AMBT molecule is adsorbed on the silver surface through the lone pair electrons of both nitrogen atoms with the molecular plane nearly vertical to the surface.     

Theoretical study of CCl(4) adsorption and hydrogenation on a Pt (111) surface

The adsorption and hydrogenation of carbon tetrachloride (CCl(4)) on a Pt (111) surface have been investigated using density functional theory (DFT). We have performed calculations on the adsorption energies and structures of CCl(4) on four different adsorption sites of a Pt (111) surface using the full adsorbate geometry optimization method. The results show that the adsorption energy of all of the potential sites is less than -17 kcal/mol, which indicates that CCl(4) is physiosorbed on a Pt (111) surface through van der Waals interactions. The dissociation and hydrogenation pathways were investigated by a transition state search. For the Pt(15), Pt(19), and Pt(25) cluster surfaces, the activation energies of dissociation obtained in this work are 15.69, 16.94, and 16.77 kcal/mol, respectively. The hydrogenation of CCl(3). was studied at the on-top site of the Pt(15) cluster, and the calculated activation energy is 5.06 kcal/mol. The small activation energies indicate that the Pt (111) surface has high catalytic activity for the CCl(4) hydrogenation reaction. In addition, the Hirshfeld population analysis reveals that the charge transfer from the Pt (111) surface to the adsorbates occurs in both the dissociation and hydrogenation pathways.     

Thermodynamic analysis of the temperature dependence of OH adsorption on Pt(111) and Pt(100) electrodes in acidic media in the absence of specific anion adsorption

The effect of temperature on the voltammetric OH adsorption on Pt(111) and Pt(100) electrodes in perchloric acid media has been studied. From a thermodynamic analysis based on a generalized adsorption isotherm, DeltaG degrees , DeltaH degrees , and DeltaS degrees values for the adsorption of OH have been determined. On Pt(111), the adsorption enthalpy ranges between -265 and -235 kJ mol(-1), becoming less exothermic as the OH coverage increases. These values are in reasonable agreement with experimental data and calculated values for the same reaction in gas phase. The adsorption entropy for OH adsorption on Pt(111) ranges from -200 J mol(-1) K(-1) (low coverage) to -110 J mol(-1) K(-1) (high coverage). On the other hand, the enthalpy and entropy of hydroxyl adsorption on Pt(100) are less sensitive to coverage variations, with values ca. DeltaH degrees = -280 kJ mol(-1) and DeltaS degrees = -180 J mol(-1) K(-1). The different dependence of DeltaS degrees with coverage on both electrode surfaces stresses the important effect of the substrate symmetry on the mobility of adsorbed OH species within the water network directly attached to the metal surface.     

氢原子在Ti(0001)表面吸附的密度泛函理论研究

用密度泛函理论研究了氢原子的污染对于Ti(0001)表面结构的影响. 通过PAW总能计算研究了p(1×1)、p(1×2)、3^1/2×3^1/2R30[deg]和p(2×2)等几种氢原子覆盖度下的吸附结构, 以及在上述结构下Ti(0001)面fcc格点和hcp格点的氢原子吸附. 结果表明, 在p(1×1)-H、p(1×2)-H、3^1/2×3^1/2R30[deg]-H和p(2×2)-H几种H原子覆盖度下, 以p(1×1)-H结构的单个氢原子吸附能为最大. 在p(1×1)-H吸附结构下, 由于氢原子吸附导致的Ti(0001)表面Ti原子层收缩的理论计算数值分别为-2.85%(hcp吸附)和-4.31%(fcc吸附), 因此实际上最有可能的情况是两种吸附方式都有一定的几率. 而实验中观察到的所谓“清洁”Ti(0001)表面实际上是有少量氢原子污染的表面. 不同覆盖度和氢分压下, 氢原子吸附的污染对Ti(0001)表面结构有极大的影响, 其表面的各种特性都会随覆盖度的不同而产生相应的变化.     

Electronic and structural properties of oligophenylene ethynylenes on Au(111) surfaces

The interaction of oligophenylene ethynylene (OPE) on the (111) surface of a gold slab resembling a self-assembled monolayer (SAM) is investigated using ab initio density functional theory calculations. The authors performed a full optimization including all atoms in the OPE and in the slab to better understand OPE adsorption on the surface. It is found that OPE has two energetically favorable adsorption sites on the Au surface with relatively different molecular geometries: the nontop site adsorption greatly modifies the (111) surface structure; however, the extensive electron interactions enable a delocalized electron density distribution, implying an improved conductivity between OPE and Au, and the top site which is 0.9 eV higher in energy than the nontop and features weaker Au-S bonds. Interestingly the on top configuration shows a strong spin imbalance along the molecule and the nontop shows a small spin imbalance on the surface. This feature is of strong interest for the development of resonators for the detection of chemical and biological agents. They have also calculated the frequency spectrum of these SAMs, which yield deformations in the gold surface yielding peak frequency shifts specific to each absorption site.     

Density functional embedded cluster study of Cu(4), Ag(4) and Au(4) species interacting with oxygen vacancies on the MgO(001) surface

Cu(4), Ag(4), and Au(4) species adsorbed on an MgO(001) surface that exhibits neutral (F(s)) and charged (F(s) (+)) oxygen vacancies have been studied using a density functional approach and advanced embedding models. The gas-phase rhombic-planar structure of the coinage metal tetramers is only moderately affected by adsorption. In the most stable surface configuration, the plane of the tetramers is oriented perpendicular to the MgO(001) surface; one metal atom is attached to an oxygen vacancy and another one is bound to a nearby surface oxygen anion. A very similar structural motif was recently found on defect-free MgO(001), where two O(2-) ions serve as adsorption sites. Following the trend of the interactions with the regular MgO(001) surface, Au(4) and Cu(4) bind substantially stronger to F(s) and F(s) (+) sites than Ag(4). This stronger adsorption interaction at oxygen vacancies, in particular at F(s), is partly due to a notable accumulation of electron density on the adsorbates. We also examined the propensity of small supported metal species to aggregate to adsorbed di-, tri- and tetramers. Furthermore, we demonstrated that core-level ionization potentials offer the possibility for detecting experimentally supported metal tetramers and characterizing them structurally with the help of calculated data.     

Adsorption dynamics of CO2 on Zn-ZnO(0001): a molecular beam study

Presented are initial S(0) and coverage Theta dependent, S(Theta), adsorption probability measurements, respectively, of CO(2) adsorption on the polar Zn-terminated surface of ZnO, parametric in the impact energy E(i), the surface temperature T(s), the impact angle alpha(i), varied along the [001] azimuth, the CO(2) flux, and the density of defects, chi(Ar(+)), as varied by rare gas ion sputtering. S(0) decreases linearly from 0.72 to 0.25 within E(i)=0.12-1.33 eV and is independent of T(s). Above E(i)=0.56 eV, S(0) decreases by approximately 0.2 with increasing alpha(i). The shape of S(Theta) curves is consistent with precursor-mediated adsorption (Kisliuk shape, i.e., S approximately const) for low E(i); above E(i)=0.56 eV, however, a turnover to adsorbate-assisted adsorption (S increases with Theta) has been observed. The initial slope of S(Theta) curves decreases thereby with increasing alpha(i), chi(Ar(+)), and T(s), i.e., the adsorbate-assisted adsorption is most distinct for normal impact on the pristine surface at low T(s) and is independent of the CO(2) flux. The S(Theta) curves have been parametrized by analytic precursor models and Monte Carlo simulations have been conducted as well. The temperature dependence of the saturation coverage shows two structures which could be assigned to adsorption on pristine and intrinsic defect sites, respectively, in agreement with a prior thermal desorption spectroscopy study. The heat of adsorption E(d) for the pristine sites amounts to 34.0-5.4Theta, whereas for adsorption on the intrinsic defect sites E(d) of approximately 43.6 kJ/mol could be estimated. Thus, a kinetic structure-activity relationship was present.     

Density functional theory study of pyrrole adsorption on Mo(110)

The objective of the present study is to identify possible adsorption configurations of pyrrole on Mo(110) using density functional theory (DFT) calculations. Several adsorption configurations were studied including pyrrole and pyrrolyl adsorption as parallel, perpendicular, and tilted adsorption modes relative to the Mo(110) surface plane. Based on the DFT calculations, pyrrole is suggested to adsorb in a parallel mode with respect to the Mo(110) surface through its pi-orbital as mu3,eta(5)-Pyr-0 degrees with an adsorption energy of -28.7 to -31.5 kcal mol(-1). The possibility of a coexisting mode where pyrrole adsorbs on the surface with a slightly tilted molecular plane as mu3,eta(4)(N,C2,C3,C4)-Pyr-5 degrees is also likely to occur, particularly at higher pyrrole coverages. The slightly tilted configuration is suggested to arise from the lateral interactions of adsorbed pyrrole on Mo(110), and not the result of a phase transformation on the surface since this requires a relatively high activation energy as indicated by additional linear synchronous transit (LST)/quadratic synchronous transit (QST) calculations. Both adsorption geometries bond to three surface Mo atoms, and Mo(110) did not promote hydrogen abstraction. Pyrrolyl adsorption on Mo(110) is energetically possible, but unlikely to occur because gas-phase hydrogen has not been previously experimentally observed as a pyrrole decomposition product on Mo(110).     

First-principles Calculations of H2O Adsorption Reaction on the GaN（0001） Surface

The adsorption and decomposition of H2O on GaN（0001） surface have been explored employing density functional theory （DFT）. Two distinct adsorption features of H2O on GaN（0001） corresponding to molecular adsorption and H-OH dissociative adsorption are revealed by our calculations. The activities of the surface reactions of H2O on GaN（0001） surface are investigated. For the stepwise processes of H2O decomposition into H2 in gas phase and adsorbed O atom （H2O（g）→H2O（chem）→OH（chem） ＋ H（chem）→2H（chem） ＋ O（chem）→H2（g） ＋ O（chem））, the first and second steps are facile and can even occur at room temperature; while the last two have high barriers and thus are difficult to proceed, especially the fourth step is endothermic. In short, H2O adsorption and decomposition into H2 in gas phase and adsorbed O atom on GaN（0001） surface are exothermic by -43.98 kcal/mol.     

周期性密度泛函理论研究NO在CuCl(111)表面上的吸附

运用广义梯度密度泛函理论(GGA)的RPBE方法结合周期平板模型,在DNP基组下,研究了NO以N端和O端两种吸附取向在CuCl(111)表面上的吸附.通过对不同吸附位和不同覆盖度下的吸附能和几何构型参数的计算和比较发现:NO吸附在CuCl(111)表面Cu原子上的top位时为稳定的吸附;覆盖度为0.25 mL时吸附比较稳定;NO的N端吸附比O端吸附更有利,N端吸附时为化学吸附,O端吸附时为物理吸附.布居分析结果表明整个吸附体系发生了从Cu原子向NO分子的电荷转移,且O端吸附时电荷转移更多.N端吸附和O端吸附时,N-O键的伸缩振动频率均红移,同时O端吸附时红移更多.     

Molecular beam induced changes in adsorption behavior of NO on NiO(111)/Ni(111)

We have examined the adsorption behavior at approximately 110 K of NO on NiO(111) overlayers prepared on a Ni(111) substrate. High-resolution electron-energy-loss spectroscopy shows fundamental changes in the vibrational spectrum for the beam dosed surface in comparison with the background dosed surface. Three vibrational peaks are observed after beam dosing, two of which are not observed after conventional background dosing. The peaks can be assigned to NO stretches for a previously observed NO state, a new NO bonding geometry, and a new NO2 surface species, previously unobserved under NO dosing. The difference is accounted for by increased NO uptake due both to kinetically activated adsorption and to increased exposure.