Adsorption of carbon monoxide on Pt{100} surfaces: dependence of the CO stretching vibrational frequency on surface coverage

We have used the ab initio cluster model approach to study the dependence of the CO stretching frequency on CO surface coverage. We have also investigated the relative importance of the various factors that can affect the position of the CO stretching band as coverage increases. Two effects can change the CO stretching frequency: the adsorbate–adsorbate dipole coupling, which is a purely physical effect, and the changes in the 2π^* CO molecular orbitals, due to the different chemical environment at higher coverages. From our vibrational analysis, we conclude that CO–CO dipole coupling is the main cause of the upward shift of the CO stretching band when the CO coverage is increased. The population of the 2π^* CO molecular orbitals does not change at any coverage within the region considered. We have also estimated the ¹²CO–¹³CO dipole coupling, which previous studies have assumed to be weak. Our results demonstrate that the ¹²CO–¹³CO dipole coupling is indeed weak compared with the ¹²CO–¹²CO dipole coupling. At a CO surface coverage of 0.5 monolayers (ML), we have calculated a band shift of 40 cm⁻¹ to higher frequency. However, we should point out that when one ¹²CO molecule is surrounded by a ¹³CO environment, the ¹²CO stretching band shifts 10 cm⁻¹ upwards. We have also computed the heat of adsorption of CO on Pt{100}-(1×1) as a function of CO coverage. The initial heat of adsorption is calculated to be about 192 kJ mol⁻¹ and then drops to 180 kJ mol⁻¹ at 0.5 ML. These results agree quite well with recent calorimetric measurements. Besides that, we have estimated that the CO–CO interaction energy at 0.5 ML is repulsive and has a value of 5 kJ mol⁻¹.     

Classical Electromagnetic Interaction of a Point Charge and a Magnetic Moment: Considerations Related to the Aharonov–Bohm Phase Shift

A fundamentally new understanding of the classical electromagnetic interaction of a point charge and a magnetic dipole moment through order v ² /c ² is suggested. This relativistic analysis connects together hidden momentum in magnets, Solem's strange polarization of the classical hydrogen atom, and the Aharonov–Bohm phase shift. First we review the predictions following from the traditional particle-on-a-frictionless-rigid-ring model for a magnetic moment. This model, which is not relativistic to order v ² /c ² , does reveal a connection between the electric field of the point charge and hidden momentum in the magnetic moment; however, the electric field back at the point charge due to the Faraday-induced changing magnetic moment is of order 1/c ⁴ and hence is negligible in a 1/c ² analysis. Next we use a relativistic magnetic moment model consisting of many superimposed classical hydrogen atoms (and anti-atoms) interacting through the Darwin Lagrangian with an external charge but not with each other. The analysis of Solem regarding the strange polarization of the classical hydrogen atom is seen to give a fundamentally different mechanism for the electric field of the passing charge to change the magnetic moment. The changing magnetic moment leads to an electric force back at the point charge which (i) is of order 1/c ² , (ii) depends upon the magnetic dipole moment, changing sign with the dipole moment, (iii) is odd in the charge q of the passing charge, and (iv) reverses sign for charges passing on opposite sides of the magnetic moment. Using the insight gained from this relativistic model and the analogy of a point charge outside a conductor, we suggest that a realistic multi-particle magnetic moment involves a changing magnetic moment which keeps the electromagnetic field momentum constant. This means also that the magnetic moment does not allow a significant shift in its internal center of energy. This criterion also implies that the Lorentz forces on the charged particle and on the point charge are equal and opposite and that the center of energy of each moves according to Newton's second law F=Ma where F is exactly the Lorentz force. Finally, we note that the results and suggestion given here are precisely what are needed to explain both the Aharonov–Bohm phase shift and the Aharonov–Casher phase shift as arising from classical electromagnetic forces. Such an explanation reinstates the traditional semiclassical connection between classical and quantum phenomena for magnetic moment systems.     

Chemical effects on vibrational properties of adsorbed molecules on metal surfaces

Vibrational properties of chemisorbed molecules on metal surfaces are studied with a focus on the coverage (θ) dependent chemical shift of the frequencies. The electronic properties of an incomplete monolayer of adsorbates are calculated by means of the coherent potential approximation, in which the electron hopping between the adsorbates (band formation effect) and the depolarization effect due to the proximity of ionized adsorbed molecules are taken into account consideration. It is found that in a weakly chemisorbed system, such as CO/Cu, the negative shift in chemical origin amounts to the positive dipole shift at low coverage. It is also shown that the variation of the back-donated charge with θ gives rise to the coverage dependent polarizability, which in turn influences the frequency shift estimated by the previous dipole coupling theory. The coverage dependent back-donation also plays a significant role in the work function change Δϕ of the substrate. The polarity of a weakly chemisorbed CO remains unchanged compared to a free CO (⁻CO⁺) so that Δϕ exhibits the initial lowering in the presence of the positive dipoles. The increase in the back-donated charge with θ causes the decrease in the effective dipole moment towards a compensation of the positive hole due to 5σ donation. A simple explanation is offered to clarify the characteristic difference of the work function change between the strongly and weakly chemisorbed CO molecules on metal surfaces. In particular, a possible origin of the work function minimum observed for CO/Cu systems is discussed in terms of the coverage dependent back-donation.     

Adsorption and reactions of CH2I2 on Ru(001) surface

The adsorption and dissociation of CH₂I₂ were studied at 110 K with the aim of generating CH₂ species on the Ru(001) surface. The methods used included X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), temperature programmed desorption (TPD), Auger electron spectroscopy (AES) and work function measurements. Adsorption of CH₂I₂ is characterized by a work function decrease (0.96 eV at monolayer), indicating that adsorbed CH₂I₂ has a positive outward dipole moment. Three adsorption states were distinguished: a multilayer (T_p=200 K), a weakly bonded state (T_p=220 K) and an irreversibly adsorbed state. A new feature is the formation of CH₃I, which desorbs with T_p=160 K. The adsorption of CH₂I₂ at 110 K is dissociative at submonolayer, but molecular at higher coverages. Dissociation of the monolayer to CH₂ and I proceeded at 198–230 K, as indicated by a shift in the I(3d_5/2) binding energy from 620.6 eV to 619.9 eV. A fraction of adsorbed CH₂ is self-hydrogenated into CH₄ (T_p=220 K), and another one is coupled to di-σ-bonded ethylene, which — instead of desorption — is converted to ethylidyne at 220–300 K. Illumination of the adsorbed CH₂I₂ initiated the dissociation of CH₂I₂ monolayer even at 110 K, and affected the reaction pathways of CH₂.     

Magnetic moment of the Δ (1232) resonance

The reaction γp → π^°γ′p has been measured with the TAPS BaF₂ calorimeter at the Mainz Microtron accelerator facility MAMI for energies between √2 = 1221–1331 MeV. Cross sections differential in angle and energy have been determined for the photon γ′ in three bins of the excitation energy. This reaction channel provides access to the magnetic dipole moment of the Δ⁺(1232) resonance and, for the first time, a value of μ_Δ+ = (2.7^+1.0_−1.3(stat) ± 1.5(syst) ± (theor)) π_N has been extracted.     

吲哚染料的电荷转移和能量转移：应用于无金属的染料敏感太阳能电池

对于应用于无金属染料敏感太阳能电池的吲哚染料用量子化学方法进行研究．对比研究吲哚染料的基态和激发态性质,揭示了随着绕丹宁环数目的增加,HOMO和LUMO的能量差减少,吸收光谱红移,但是束缚能增加,跃迁偶极矩减少;依据电荷差分密度,电荷和能量从苯乙烯转移到吲哚环和绕丹宁;电子空穴相干性主要表现在吲哚环和绕丹宁环,对于吲哚染料系统,存在一个绕丹宁环的体系的激子数目为30个原子,带有两个绕丹宁环的体系激子数目有40个原子．理论计算结果可以应用于无金属的染料敏感太阳能电池的吲哚染料的计算机辅助设计中．     

First principles study of carrier activity,lifetime and absorption spectrum to investigate effects of strain on the photocatalytic performance of doped ZnO

Doping of isovalent (S, Se, and Te) elements in ZnO is a new doping method. However, the factors affecting the photocatalytic performance of a doped system by triaxial strain are often ignored. In this study, we have applied strain on model and performed first-principle calculation to investigate the effect of triaxial strain on the stability of the doped system, red shift of the absorption spectrum, electric dipole moment, and carrier lifetime. Calculation results showed that all doped systems exhibited high binding energy and stability under unstrained conditions. However, when the applied strain was increased, the energy of all the systems increased, and the stability decreased. The stability, red shift of absorption spectrum, electric dipole moment, and carrier lifetime of all doped systems were studied. When the tensile strain was 5%, the red shift of the absorption spectrum and the electric dipole moment of the doped system (Zn₃₆SO₃₅) were the largest. Moreover, the carrier lifetime of the doped system (Zn₃₆SO₃₅) was the longest. Considering the red shift of the absorption spectrum, electric dipole moment, and carrier lifetime, the photocatalytic performance of the doped system (Zn₃₆SO₃₅) was the best, when the tensile strain was 5%.     

Comparison of cross sections in high resolution electron energy loss spectroscopy and infrared reflection spectroscopy

Electron energy losses and absorption of infrared radiation are both caused by the dipole moment of the surface vibration. A comparison of absolute intensities between both techniques should therefore be possible. In this paper the appropriate formulas are derived. For the adsorption system CO on Pt(111) which has been investigated by both techniques a perfect agreement is found. For a number of adsorbate systems the effective ionic charge is calculated from previously published electron energy loss data.     

哈龙1211分子在外电场中的物理特性研究

采用密度泛函理论,在B3LYP/6-311++G(d,p)基组水平上对分子进行优化,研究了在不同外电场下,哈龙1211分子的键长、体系总能量、偶极矩、能级、能隙、电荷分布和红外光谱的变化规律.计算结果表明,电场方向不同,键长的变化趋势也不同.随着外电场(-0.02 a.u.-0.03 a.u.)的增加,C-Br间的键长随x轴方向电场的增加可能先趋于断裂,而C-Cl间的键长随y轴方向电场的增加可能最先趋于断裂,这对利用外电场解离哈龙1211分子有着重要意义.体系总能量和能隙随着外电场的增加先增大后减小,而偶极矩的变化趋势相反.另外,随着电场的增加,红外光谱的最强峰先发生蓝移再发生红移.     

Multipole-Bound Molecular Negative Ions

 Within the framework of a simple electrostatic model, as compared to recent experimental results, we here discuss the stability of very weakly bound molecular negative ions. In contrast with the case of conventional valence anions, the excess electron is then located in a very diffuse orbital and is mainly bound by electrostatic dipolar, quadrupolar, and polarization forces, at large distances from the neutral molecular core. By fitting a single repulsion parameter of the model to the available experimental data, it is possible to make quantitative predictions of the excess-electron binding energies in these species. Critical values of the dipole moment, quadrupole moment or polarizability required for the observation of stable multipole-bound negative ions are predicted and compared to available experimental data and ab initio calculations. Received October 24, 2001; accepted for publication November 16, 2001     

外电场作用下BrCl分子的物理特性与光谱

采用HF （Hartree-Fock）方法,在6-31+G（d,p）基组水平上优化不同外电场（0~0.035 a.u.）下氯化溴分子的基态稳定构型,在此基础上计算氯化溴分子的分子结构、偶极矩、分子总能量、分子键长、分子电荷分布、分子能隙、红外光谱及解离势能面等.结果表明：随着Z轴（平行于Br-Cl连线）方向外电场的增加（0~0.035 a.u.）,分子总能量先小幅度增加后又降低,键长先减小后增大,分子偶极矩先减小后单调增加,原子电荷分布递增,分子能隙逐渐减小,分子红外光谱先蓝移后红移.通过对解离势能面的计算分析发现,强度为0.045 a.u.的外电场使得Br-Cl键断裂而降解,该结果对氯化溴进行电场降解提供参考依据.     

The concept of weak polarity: an application to the SrTiO3(001) surface

We propose the term “weak polarity” to characterize the electrostatic properties of some ternary (or more complex) insulating compound slabs, which are not fully ionic and in which covalency (i.e. anion-cation electron sharing) is responsible for the presence of a non-vanishing macroscopic dipole moment perpendicular to the surface. We exemplify this situation by the SrTiO₃(001) surface, which we study by means of a semi-empirical Hartree-Fock approach. The bond-breaking processes at the surface are shown to yield the charge redistribution required for the cancellation of the macroscopic electrostatic field. There is no need for strong modifications of the electronic structure such as the surface metallization predicted on the polar stoichiometric MgO(111) surface.     

STM and chemistry: a qualitative molecular orbital understanding of the image of CO on a Pt surface

Theoretical calculations of STM images for isolated carbon monoxide on Pt(111) have been performed. These simulations are directly comparable to experimental data from Eigler's group. They also confirm a strong site dependence of the STM molecular contrast and assign the two experimental STM forms of CO with two distinct binding sites (the top and the bridge sites) which have already been well-characterised by other surface techniques. Moreover, the approach used here allows a detailed understanding of the electronic origin of the STM molecular pattern. Hence, we demonstrate that the CO STM pattern results from the superposition, with interference effects, of two current contributions. The direct through space tunneling process between the tip and the metal surface is decreased by the presence of the adsorbate molecule, but this depression in the current is more or less compensated, depending on the binding site, by the tunnel current mediated by the molecular levels of the adsorbate. The frontier π orbitals of CO have a small contribution to the current and the σ framework has the major influence with the 5σ lone pair (HOMO of CO) and also the low-lying 3σ. These two MO contributions, however, show a destructive interference effect, and this, together with the absence of π current, is responsible for the weak amplitude of the CO STM image.     

哈龙1211分子在外电场中的物理特性研究

采用密度泛函理论,在B3LYP/6-311++G(d,p)基组水平上对分子进行优化,研究了在不同外电场下,哈龙1211分子的键长、体系总能量、偶极矩、能级、能隙、电荷分布和红外光谱的变化规律。计算结果表明,电场方向不同,键长的变化趋势也不同。随着外电场(-0.02a.u.—0.03a.u.)的增加,C-Br间的键长随x轴方向电场的增加可能先趋于断裂,而C-Cl间的键长随y轴方向的增加可能最先趋于断裂,这对利用外电场解离哈龙1211分子有着重要意义。体系总能量和能隙随着外电场的增加先增大后减小,而偶极矩的变化趋势相反。另外,随着电场的增加,红外光谱的最强峰先发生蓝移再发生红移。     

Some laws of polarization and dispersion of a drop in an electrostatic field

The laws of distribution among contributions in various interactions to the total polarization energy of a conductor in a uniform electrostatic field was analyzed. It is shown that in a closed system, spontaneous shape variations of a liquid conductor with a free surface in an external magnetic field are possible only if they are accompanied by an increase in the conductor dipole moment. Variations of the intrinsic energy of a conductor are studied by the example of a conductive liquid drop in the case where a drop affected by a polarization charge becomes unstable. Analytical expressions defining the sizes and charges of the droplets ejected out of the initial drop under the conditions of instability are derived.     

(MgO)(-)(n) (n = 1-5) clusters: multipole-bound anions and photodetachment spectroscopy

Photoelectron spectra of (MgO)(-)(n) (n = 1-5) reveal a surprising trend: The electron binding energy decreases from n = 1 to 4, and then increases from 4 to 5. Ab initio calculations suggest this pattern is related to the electrostatic interaction between the extra electron and the charge distribution of the neutral cluster. This interaction is significant in MgO (-) and (MgO)-5, for which the lowest nonvanishing multipole moment (LNM) is a dipole; it is smaller for (MgO)-2 and (MgO)-3, for which a quadrupole is the LNM; and it is the smallest for (MgO)-4, for which an octopole is the LNM. The cubic (MgO)-4 is the first octopole-bound anion yet observed experimentally and characterized theoretically.     

Spectral Investigations of Solvatochromism and Preferential Solvation on 1,4-Dihydroxy-2,3-Dimethyl-9,10-Anthraquinone

Solvatochromic and preferential solvation of 1,4-dihydroxy-2,3-dimethyl-9,10-anthraquinone (DHDMAQ) have been investigated using optical absorption and fluorescence emission techniques. Optical absorption spectra of DHDMAQ in different solvents show the intra molecular charge transfer band in the region 400–550nm. The observed blue shift with solvent polarity indicates the delocalisation of the excited state, owing to reduction in quasiaromaticity of the chelate rings formed by intra molecular hydrogen bonds, due to electrostatic or hydrogen bonding interaction. This is also confirmed by the observed low oscillator strength and the transition dipole moment. The observed quantum yield of DHDMAQ in different solvents is due to the inter molecular hydrogen bond in the excited state in addition to the intra molecular hydrogen bond. It also reveals from the low oscillator strength, which indicates that the radiative decay is low. Excited state dipole moment of DHDMAQ is calculated by solvatochromic data and it shows a lower value than ground state dipole moment. The preferential solvation parameter shows that in dimethyl formamide (DMF) + ethanol mixture, the DHDMAQ is preferentially solvated by ethanol in DMF rich region and by DMF in ethanol rich region. In the case of DMF + dichloromethane mixture DHDMAQ is preferentially solvated by DMF.     

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.     

盐离子对蛋白质带电特性的影响

本文应用分子理论,研究盐离子对蛋白质带电特性的影响,理论模型考虑蛋白质与阴离子的结合作用。研究发现,由于蛋白质与阴离子的结合,距离蛋白质表面附近处的阴离子被吸附在了蛋白质表面,在距离蛋白质表面附近区域,阴离子分布较少。通过计算体系中的静电势,我们发现,在距离蛋白质表面附近,静电势呈现了较大的负值,带正电荷的阳离子感受到静电吸引,会出现在距离蛋白质表面附近的区域,这会使得在距离蛋白质表面附近的区域,阳离子数目增多。这样,在不同阴离子浓度、以及阴离子与蛋白质不同结合能条件下,阴离子会在不同程度上影响蛋白质的带电特性、影响体系中的静电特性。通过考察不同结合能条件下,蛋白质表面电荷面密度随阴离子浓度的变化关系还发现,较大的结合能会使得阴离子与蛋白质结合增快,蛋白质表面会呈现从正电荷态向负电荷态的转变。理论结果符合实验观测,由此表明,盐离子与蛋白质的结合导致蛋白质表面带电特性的改变,是盐离子影响蛋白质带电特性的本质。     

Polarization and charge transfer during the dissociation of H2 on Al(110)

We present a density functional calculation within the generalized gradient approximation of the H₂ induced dipole moment along the reaction path for dissociation outside an Al(110) surface. The dipole moment is found to change sign during the adsorption process, being positive far from the surface and negative closer in where the antibonding H₂ level is being filled. Assuming this variation to be qualitatively similar for other surfaces, we can classify the effect of an electrostatic field or an adsorbed alkali atom on the adsorption process according to whether the barrier to adsorption is in the entrance channel or the exit channel. The electrostatic interaction model is shown to qualitatively explain why adsorbed alkalies promote the dissociation of