Surface states and negative electron affinity in polyethylene

First-principles calculations are used to investigate the electronic properties of the surfaces of polyethylene. The calculations support the experimental evidence of a negative electron affinity, with calculated values of -0.17 eV and -0.10 eV for surfaces with chains perpendicular and parallel to the surface normal, respectively. Both surfaces exhibit a surface state with binding energy -1.2 +/- 0.5 eV with respect to the bulk polyethylene conduction band minimum. Implications of these findings on spectroscopy, as well as on the transport and aging properties of polyethylene for high-voltage applications, are discussed.     

Ab initio calculations of CO physisorption on ceria(1 1 1)

Applying the method of increments, we have performed MP2 and CCSD(T) calculations for the physisorption of CO on a cerium site on the ceria(1 1 1) surface. Our calculations predict an interaction energy of −0.28 eV. We have compared our calculations to previous CCSD(T) calculations for the physisorption of CO on a cerium site on the ceria(1 1 0) surface and found a difference in the interaction energy that is related to the different structure of the two surfaces. On the ceria(110) surface only 30% of the interaction energy originate from electron correlation effects, but on the ceria(111) surface almost the entire binding energy (80%) is due to electron correlation effects. Analyses of the interaction energy contributions show that most of the electron correlation part originates from the interaction of CO with the O ions in the topmost surface layer.     

On the possibility of single-electron transfer during alkaline hydrolysis of sulfophthalides

The previously observed generation of radical products during the alkaline hydrolysis of diphenylsulfophthalide (DPSP) and polydiphenylenesulfophthalide in dimethyl sulfoxide (DMSO) is indicative of the involvement of single-electron transfer (SET) in thses processes. The possibility of SET from the hydroxide ion (HI) to the sulfophthalide molecule is determined by the ratio between the ionization potential (IP) of the HI and electron affinity (EA) of the sulfophthalide. According to B3LYP/6-311+G(d,p) calculations for DPSP, EA _ver = 0.06 eV and EA _ad = 0.58 eV, whereas EA _eff = 2.13 eV (with consideration of the C-O bond rupture in the sulfophthalide cycle). Such a value of the electron affinity cannot ensure SET from the HI, the ionization potential of which in DMSO reaches ∼5.25 eV. The EA of the carbocation formed from DPSP is 6.44 eV as calculated in the same approximation. A mode of SET from the HI to the carbocation intermediate formed during DPSP heterolysis in DMSO is proposed. Two possible modifications of the electron donor are considered. The possibility of occurrence of SET from the dimsyl ion and HI-DMSO complex is evaluated using the G3B3 method. The ionization potential of the dimsyl ion in DMSO is almost 1 eV lower than the IP of the HI, which makes the former a preferential donor in comparison with the HI. The ionization potential of the weak HI-DMSO complex even exceeds the IP of the HI; i.e., complexation does not improve the electron-donor properties of the hydroxide ion.     

磁瓶式光电子能谱和速度成像光电子能谱对APS-(A=C14H10,蒽)的研究:电子结构,APS·的自旋轨道耦合和APS-的自旋偶极态

Gaseous dibenzo-7-phosphanorbornadiene P-sulfide anions APS^-(A=C₁₄H₁₀ or anthracene) were generated via electrospray ionization, and characterized by magnetic-bottle photoelectron spectroscopy, velocity-map imaging (VMI) photoelectron spectroscopy, and quantum chemical calculations. The electron affinity (EA) and spin-orbit (SO) splitting of the APS^· radical are determined from the photoelectron spectra and Franck-Condon factor simulations to be EA=(2.62±0.05) eV and SO splitting=(43±7) meV. VMI photoelectron images show strong and sharp peaks near the detachment threshold with an identical electron kinetic energy (eKE) of 17.9 meV at three different detachment wavelengths, which are therefore assigned to autodetachment from dipole-bound anion states. The B3LYP/6-31++G(d,p) calculations indicate APS^· has a dipole moment of 3.31 Debye, large enough to support a dipole-bound electron.     

The aluminum arsenides Al<Subscript>m</Subscript>As<Subscript>n</Subscript> (m + n = 2–5) and their anions: Structures,electron affinities and vibrational frequencies

Geometries, electronic states and electron affinities of Al_mAs_n and Al_mAs _n (m+n=2–5) clusters have been examined using four hybrid and pure density functional theory (DFT) methods. Structural optimization and frequency analyses are performed using a 6-311+G(2df) one-particle basis set. The geometries are fully optimized with each DFT method independently. The three types of energy separations reported in this work are the adiabatic electron affinity (EA_ad), the vertical electron affinity (EA_vert), and the vertical detachment energy (VDE). The calculation results show that the singlet structures have higher symmetry than that of doublet structures. The best functional for predicting molecular structures was found to be BLYP, while other functionals generally underestimated bond lengths. The largest adiabatic electron affinity, vertical electron affinity and vertical detachment energy, obtained at the 6-311+G(2df)/BP86 level of theory, are 2.20, 2.04 and 2.27 eV (AlAs), 2.13, 1.94 and 2.38 eV (AlAs₂), 2.44, 2.39 and 2.47 eV (Al₂As), 2.09, 1.80 and 2.53 eV (Al₂As₂), 2.01, 1.57 and 2.36 eV (AlAs₃), 2.32, 2.11 and 2.55 eV (Al₂As₃), 2.40, 1.45 and 3.26 eV (AlAs₄), 1.94, 1.90 and 2.07 eV (Al₄As), respectively. However, the BHLYP method gives the largest values for EA_ad and EA_vert of Al₃As and EA_ad of Al₃As₂, respectively. For the vibrational frequencies of the Al_nAs_m series, the B3LYP method produces good predictions with the average error only about 10 cm^-1 from available experimental and theoretical values. The other three functionals overestimate or underestimate the vibrational frequencies, with the worst predictions given by the BHLYP method.     

Electron emission from diamondoids: a diffusion quantum Monte Carlo study

We present density-functional theory (DFT) and quantum Monte Carlo (QMC) calculations designed to resolve experimental and theoretical controversies over the optical properties of H-terminated C nanoparticles (diamondoids). The QMC results follow the trends of well-converged plane-wave DFT calculations for the size dependence of the optical gap, but they predict gaps that are 1-2 eV higher. They confirm that quantum confinement effects disappear in diamondoids larger than 1 nm, which have gaps below that of bulk diamond. Our QMC calculations predict a small exciton binding energy and a negative electron affinity (NEA) for diamondoids up to 1 nm, resulting from the delocalized nature of the lowest unoccupied molecular orbital. The NEA suggests a range of possible applications of diamondoids as low-voltage electron emitters.     

The ClO4 radical: a theoretical study on ground and excited states

In agreement with previous studies, the ground state of ClO₄ has been confirmed to be X²B₁. Vertical excitation energies and oscillator strengths were calculated by MRCI methods for doublet and quartet states of ClO₄. The highest oscillator strength was found for 1²A₁ at 2.95 eV. This state has been identified as the upper state seen by Kopitzky and co-workers in the absorption spectrum of ClO₄. Two higher states, 2²A₁ and 3²A₁, at 4.19 and 8.12 eV, respectively, also have relatively high oscillator strengths. Rydberg states start at about 9.5 eV. Geometry optimizations were performed by DFT and CCSD(T) methods. After extensive testing, the B3LYP density functional, together with the 6-311 + G(3df) basis set were chosen for calculations. Optimized geometries of seven excited states were obtained. The adiabatic excitation energy of 1²A₁ (2.40 eV) agrees closely with the observed band origin at 2.46 eV. Three excited states have one or two imaginary vibrational modes. Electron affinity and heat of formation of ClO₄ agree with literature values. None of the quartet states was found to be stable.     

丝氨酸异构体的电子-分子形状共振态及其解离动力学理论研究

Shape resonances of electron-molecule system formed in the low-energy electron attachment to four low-lying conformers of serine (serine 1, serine 2, serine 3, and serine 4) in gas phase are investigated using the quantum scattering method with the non-empirical model potentials in single-center expansion. In the attachment energy range of 0-10 eV, three shape resonances for serine 1, serine 2, and serine 4 and four shape resonances for serine 3 are predicted. The one-dimensional potential energy curves of the temporary negative ions of electron-serine are calculated to explore the correlations between the shape resonance and the bond cleavage. The bond-cleavage selectivity of the different resonant states for a certain conformer is demonstrated, and the recent experimental results about the dissociative electron attachment to serine are interpreted on the basis of present calculations.     

A prospective DFT study for assembling highly reactive clusters based on lithium boranes and alanates

In this work, first-principles calculations using the density functional theory are performed to study the structure, stability and electronic properties of lithium borohydrides (boranes) and lithium aluminohydrides (alanates). With the attachment of BH₄ and AlH₄ complexes to the Li atom, the electron affinity increases to 5.22 eV and 4.34 eV, in the clusters Li(BH₄)₂ and Li(AlH₄)₂, respectively, which indicate superhalogen behaviour. For the alanates, by decorating the Li atom with the superhalogen moiety, the electron affinity increases to 4.64 eV, in the large-sized cluster Li[Li(AlH₄)₂]₂. The substitution of Al for B leads to larger NBO charges on the H atoms, as a result of the electron- donating character of the Al atom. The results show that, besides larger gravimetrical storage capacities, the boranes also have higher electron affinities than the alanates in the large-sized clusters. The significant HOMO-LUMO differences indicate that the new moieties, which are highly reactive, are chemically very stable species.     

Measurement of the HeI 4471 Å profile at an electron density of 1015 cm−3

The profile of the HeI 4471 Å line and its forbidden component was measured using a pulsed arc plasma (electron density 10¹⁵ cm^?3, temperature 1·5 eV) as the light source. The profile is in good agreement with recent calculations in which the ion motion has been taken into account.     

Measurement of Stark broadened profile of He(II) 4686A

Stark broadened profiles of the He(II) 4686A line were measured using a Z-pinch plasma as source. The electron density was determined from the halfwidth of the He(I) 3889 line and the temperature from the intensity ratio of the He(II) 4686 and the He(I) 3889 lines. The electron densities covered the range 0.5?2.3×10¹⁷ cm³ and the electron temperature was 4 eV. The plasma homogeneity was checked by varying the length of the column observed. The experimental profiles are in better agreement with the recent calculations of Greene than with the earlier calculations of Keeple.     

Intrinsic electron accumulation at clean InN surfaces

The electronic structure of clean InN(0001) surfaces has been investigated by high-resolution electron-energy-loss spectroscopy of the conduction band electron plasmon excitations. An intrinsic surface electron accumulation layer is found to exist and is explained in terms of a particularly low Gamma-point conduction band minimum in wurtzite InN. As a result, surface Fermi level pinning high in the conduction band in the vicinity of the Gamma point, but near the average midgap energy, produces charged donor-type surface states with associated downward band bending. Semiclassical dielectric theory simulations of the energy-loss spectra and charge-profile calculations indicate a surface state density of 2.5 (+/-0.2)x10(13) cm(-2) and a surface Fermi level of 1.64+/-0.10 eV above the valence band maximum.     

Measurement of the two-loop lamb shift in lithiumlike U89+

Using the SuperEBIT electron beam ion trap, we have measured the 2s(1/2)-2p(1/2) transitions in U88+ and U89+. The measured value of 280.645 +/- 0.015 eV for Li-like U89+ improves the available precision by nearly an order of magnitude and establishes a new benchmark for testing the total QED contribution to the transition energy within a fractional accuracy of 3.6 x 10(-4). We infer a value for the 2s two-loop Lamb shift in U89+ of -0.23 eV, from which we estimate a value of -1.27 eV for the 1s two-loop Lamb shift in U91+.     

Low-temperature helium defectoscopy and interaction of helium with ions of cerium gadolinium ceramics Ce<Subscript>0.8</Subscript>Gd<Subscript>0.2</Subscript>O<Subscript>1.9</Subscript> with a submicrocrystalline structure

The concentration of unbound neutral anion vacancies in cerium gadolinium ceramics Ce_0.8Gd_0.2O_1.9 with a submicrocrystalline structure has been determined using low-temperature helium defectoscopy at temperatures ranging from 613 to 773 K and at saturation pressures from 0.05 to 12 MPa. It has been found that the energy of dissociation of impurity-vacancy complexes is 1.1 ± 0.2 eV, and the energy of dissolution of helium in defects is −0.8 ± 0.2 eV. The obtained results have been compared both with the experimental data on the energy of interaction between helium and ions of the cerium gadolinium ceramics and with the results of the quantum-chemical calculations. It has been demonstrated that the anomalously low value of the energy of helium dissolution in the studied ceramic samples is determined by the chemical interaction of helium with the nearest environment of the cerium cations.     

f Electron contribution to the change of electronic structure in CeRu2Si2 with temperature: a Compton scattering study

High resolution Compton profiles have been measured in the single crystal of CeRu(2)Si(2) above and below the Kondo temperature to elucidate the change of the Ce-4f electron from localized to itinerant states. Two-dimensional electron occupation number densities projected on the first Brillouin zone, which are obtained after a series of analyses, clearly specify the difference between itinerant and localized states. The contribution of Ce-4f electrons to the electronic structure is discussed by contrast with a band calculation.     

Cross section for single ionization of magnesium by electron impact

The direct single ionization cross sections for electron scattering with magnesium are calculated by applying a complex equivalent-local polarization potential in momentum space from the ionization threshold (7.64 eV) to 500 eV. The present results are in excellent agreement with the recent experimental measurements in both shape and magnitude. The present results are also compared with other theoretical calculations.     

The angular distribution of the 3p electrons and the partial cross section of the 3s electrons of argon from threshold to 70 eV

The angular distribution parameter β has been measured for the argon 3p electrons in the energy range 0–70 eV above threshold using a synchrotron light source. The absolute photoionization cross section of argon 3s electrons has also been determined in the 0–60 eV region above threshold. Both sets of data are compared with recent theoretical calculations which include electron correlation effects.     

Electron-irradiation-induced radiolytic oxygen generation and microsegregation in silicon dioxide polymorphs

The first direct in situ observations of the production and microsegregation of radiolytic interstitial oxygen resulting from electron beam irradiation of crystal and amorphous oxygen deficient SiO2 polymorphs has been made using cathodoluminescence (CL) microanalysis (spectroscopy and microscopy). Previously unreported near-infrared CL emission is observed at 0.968+/-0.003 eV from crystal alpha-SiO2 (quartz) and at 0.971+/-0.003 eV from amorphous a-SiO2 (fused quartz and silica glasses) at 290 K. The energy and width of the near-infrared CL emission from electron-irradiated alpha-SiO2 polymorphs is consistent with the O2 (1)Delta(g)-->(3)Sigma(-)(g) transition associated with molecular oxygen.     

Observation of positive and small electron affinity of Si-doped AlN films grown by metalorganic chemical vapor deposition on n-type 6H–SiC

We have investigated the electron affinity of Si-doped AlN films(N_(Si)= 1.0 × 10~(18)–1.0 × 10_(19)cm~(-3)) with thicknesses of 50, 200, and 400 nm, synthesized by metalorganic chemical vapor deposition(MOCVD) under low pressure on the ntype(001)6H–SiC substrates. The positive and small electron affinity of AlN films was observed through the ultraviolet photoelectron spectroscopy(UPS) analysis, where an increase in electron affinity appears with the thickness of AlN films increasing, i.e., 0.36 eV for the 50-nm-thick one, 0.58 eV for the 200-nm-thick one, and 0.97 e V for the 400-nm-thick one.Accompanying the x-ray photoelectron spectroscopy(XPS) analysis on the surface contaminations, it suggests that the difference of electron affinity between our three samples may result from the discrepancy of surface impurity contaminations.     

二乙酰分子内价轨道4ag+4bu的电子动量谱学研究

在高分辨率(ΔE=115eV, Δp≈01a.u.)电子动量谱仪上获得了二乙酰分子(d iacetyl)最内价轨道4ag_g+4bu_u的电离能谱和动量谱的实验结果， 并用Hartree-Fock和密度泛函理论方法做了理论计算.实验结果与理论计算符合较好. 关键词： 二乙酰 内价轨道 电离能 电子动量谱