Electronic properties of metal clusters (Ni13 to Ni87) and implications for chemisorption

First principles calculations of the electronic properties of Ni clusters (up to Ni₈₇) are reported. It is found that the ionization potential (IP) converges to bulk values (work function) by Ni₄₃, whereas the electron affinity (EA) is off by 2.5 eV, even for Ni₈₇. The conduction band of ～16 eV appears converged by Ni₈₇. It is found that the electron density for surface atoms is significantly lower than the bulk value. The significance of these results for chemisorption on small metallic clusters and for modelling of chemisorption on bulk surfaces is discussed.     

Ionisation energy,electron affinity,and mass spectral decomposition mechanisms of RDX isomers upon electron attachment and electron ionisation

ABSTRACT

The structures, ionisation energies (IE), and electron affinities (EA) of 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX) isomers upon loss and gain of an electron were calculated using density functional theory (DFT) methods. The adiabatic electron affinities (EA_ad) range from 1 to 2 eV. The vertical detachment energies are between 1.3 and 4.0 eV. The adiabatic ionisation energies (IE_ad) are in the 9.9–10.2 eV range. The vertical ionisation energies are in the 10.4–10.9 eV range. It is shown that NO₂^?/NO₂ loss would be common in anions and cations, respectively. Isomerisation and N—N bond dissociation accompany cation and anion formation, respectively. The suggested mass spectral fragmentation products for the cations along the S₀ surface are 84, 130, and 176 amu, in agreement with earlier mass spectrometry studies.     

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.     

XF3 (X=N,P,As)价层电离势的运动方程耦合团簇理论计算

采用运动方程单双取代耦合团簇理论(EOM-CCSD)对XF₃(X=N,P,As)的价层垂直离势(VIP)进行了系统计算,同时对称匹配团簇组态相互作用(SAC-CI)、外价层格林函数(OVGF)以及部分三阶近似(P3)方法也被应用到目前计算.与已有的实验结果比较表明:EOM-CCSD计算的价层垂直电离势整体上与SAC-CI结果相近,而优于OVGF和P3理论结果,在整个价层上,EOM-CCSD结果与实验值总体差距约0.2 eV, 在外价层这种差距相对较小,在内 关键词： XF₃(X=N;P;As)')" href="#">XF₃(X=N;P;As) 垂直电离势 运动方程耦合团簇理论     

Photoelectron Spectroscopy of Nickel, Palladium, and Platinum Oxide Anions

The 364-nm negative ion photoelectron spectra of XO and OXO molecules (X=Ni, Pd, and Pt) are reported. The spectra yield the electron affinities (EAs): EA(NiO)=1.455±0.005 eV; EA(PdO)=1.672±0.005 eV; EA(PtO)=2.172±0.005 eV; EA(ONiO)=3.043±0.005 eV; EA(OPdO)=3.086±0.005 eV; EA(OPtO)=2.677±0.005 eV. In addition, for the diatomics, transitions from the anion X?²Π_3/2 and X?′²Π_1/2 states into neutral X?³Σ⁻, ³Π, and for NiO and PdO, ¹Π, are assigned. Several states have been reassigned from those in the existing literature. Anion ²Π_3/2-²Π_1/2 spin-orbit splittings are measured, as are neutral ³Π₂-³Π₁ spin-orbit splittings: the XO ³Π ₂-³Π₁ splittings increase from 405±30 cm⁻¹ (NiO) to 805±30 cm⁻¹ (PdO) to 3580±40 cm⁻¹ (PtO). A bond length shortening of 0.03±0.01 Å is measured upon electron detachment from NiO⁻, resulting in an anion bond length of 1.66±0.01 Å. The bond length does not change upon electron detachment from PdO⁻ using 3.4-eV photons. The Pt-O bond length decreases by 0.035±0.010 Å in the ³Π₁←²Π_3/2 transition. The spectrum of OPtO displays a significantly more extended vibrational progression than those of ONiO or OPdO, and the O-Pt bond length is found to decrease by 0.07±0.01 Å upon electron detachment. The spectra support the view that the Ni-O bond is largely ionic, the Pd-O bond is somewhat less so, and the Pt-O bond displays a substantial covalent character.     

Excitation-autoionization cross sections and rate coefficients for Ga-like ions

Detailed level-by-level calculations of cross sections and rate coefficients for electron impact direct and indirect ionization of ions belonging to the GaI isoelectronic sequence (ground 3d ¹⁰4s ²4p) have been performed. The cross sections are presented in the energy range near the threshold for the five ions Kr⁵⁺, Mo¹¹⁺, Xe²³⁺, Pr²⁸⁺ and Dy³⁵⁺. The rate coefficients are given for ions from Kr⁵⁺ to U⁶¹⁺ in the GaI sequence at seven electron temperatures (kT _e = 0.1E _I , 0.3E _I , 0.5E _I , 0.7E _I ,E _I , 2E _I and 10E _I , where E _I is the first ionization energy). The calculations include the contribution of direct ionization (DI) calculated using the Lotz formula approximation and the contributions of excitation-autoionization (EA) computed in the framework of the distorted wave (DW) approximation for the 4s-nl, 3d-nl and 3p-nl resonant inner-shell excitations. The ionization enhancement due to the EA channels is presented as a function of Z along the GaI isoelectronic sequence. The present results show the great importance of the EA processes; an ionization enhancement factor of up to 10 is predicted for instance for La²⁶⁺ (Z = 57) at electron temperature of coronal equilibrium maximum abundance.     

Enhanced optical nonlinearity based on silicon ring

The photoelectron spectrum of ethylene is studied using coupled cluster methods, including an existing ambiguity in what are reported to be its experimental vertical ionization potentals. Two complementary methods are used for generating the ionization potentials: δE CCSD(T) and IP-EOM-CCSD. The adiabatic IP of the neutral molecule in the ground state is well known and widely accepted to be 10.5122eV. The basis set extrapolated adiabatic IPS with zero-point corrections are 10.46 eV and 10.56 eV, respectively, but a vibronic coupling between the ground state cation and its first excited state can reduce these values by ～0.03 eV. From an exponential basis set extrapolation the vertical ionization potentials are predicted to be 10.8 eV (B_3u, 13.2eV (B_3g 15.0eV (A_g), 16.4eV (B_2u), and 19.6eV (B_1u) ±0.1 eV.     

Estimation of the ionization potential for polyhalogenated hydrocarbons by weakest bound potential method

The weakest bound potential method was proposed to estimate the ionization potential (IP) of polyhalogenated methanes, that is, the model IP = aχ_ve + bPEI_fi + c was developed, in which χ_ve is molecular electronegativity calculated by valence electrons equilibration method, and polarizability effect index (PEI)_fi is the influence of polarizability effect. The result indicates that the model is reasonable and effective to predict the IP for polyhalogenated methanes. Besides, the quantum chemistry method, the MOPAC AM1 method, and the density functional theory (B3LYP) method were employed to calculate the IP values of the same polyhalogenated methanes, and those results were less than that of the weakest bound potential method. Furthermore, the experimental values of 67 polyhalogenated hydrocarbons were correlated with the parameters χ_ve and PEI_fi. The regression results show a good correlation (R = 0.988), and the average absolute error between the experimental values and the calculated values is only 0.10 eV. Copyright © 2011 John Wiley & Sons, Ltd.     

Insights into unusual stability of 5‐membered‐ring endocyclic benzyl carbocations in aqueous solution

The acyclic o‐oxygen benzyl carbocation 1 , the 6‐membered‐ring endocyclic o‐oxygen benzyl carbocation 2 , and the 5‐membered‐ring endocyclic o‐oxygen benzyl carbocation 3 were used as model compounds to get insights into the general phenomenon for the unusual stability of the 5‐membered‐ring endocyclic benzyl carbocations in aqueous solution. The hydride‐ion affinities of 1 , 2 , and 3 in gas phase, acetonitrile, and DMSO were calculated and compared by the density functional theory method, and 3 isodesmic reactions were designed to confirm their thermodynamic stability. What we found is that the 5‐membered‐ring endocyclic o‐oxygen stabilizes the benzyl carbocation 3 less than the acyclic o‐oxygen stabilizes the benzyl carbocation 1 in gas phase because of ring strain and through‐bond induction. However, the high solvation energies of the 5‐membered‐ring endocyclic o‐oxygen benzyl carbocation 3 not only offset the destabilizing effects of ring strain and through‐bond induction but also make it even more stable than the acyclic o‐oxygen benzyl carbocation 1 in polar solvents like acetonitrile, DMSO, and water.     

Ladungsaustausch-Reaktionen einiger negativer Ionen mit O2 und die Elektronenaffinität des O2

Investigations on the energy dependence of the cross section of charge transfer reactions with negative ions yield evidence on the relative values of the electron affinities of the colliding particles. It is shown that H^?+ O₂ and SO^? + O₂ are exothermic and that ND ₂ ^? + O₂ is anendothermic reaction. With EA(H)=0.776eV, EA(SO)=1.05eV and EA (ND₂) ≈ 1.2 eV we find 1.05 eV < EA (O₂) < ≈ 1.2 eV.     

Photoelectron and electron impact spectrum of HCN

The electronic structures of HCN and DCN have been determined by examining high resolution He(I) photelectron spectra of HCN and DCN, He(II) photoelectron spectrum of HCN, and the electron impact energy loss spectra of HCN and DCN. The present investigation supports an earlier assignment of the orbital sequence in HCN. New vibrational data are presented and the Rydberg series and valence transitions are reinvestigated. The adiabatic ionization energies for the 1π and 5σ orbitals in HCN are found to be 13.607 ± 0.002 eV and 14.011 ± 0.003 eV respectively.As mentioned above the investigation of the Rydberg series indicated that the first IP at 13.607 eV is the 1π ionization and the second IP at 14.011 eV is the 5σ ionization. A comparison of the experimental and theoretical intensity ratio between the two first PES progressions also supports this assignment. It is further supported by the fact that in the second IP the ν₃ vibration frequency is not changed as much as it is in the first IP, which is in agreement with the PES of N₂ and CO. The analysis of the bending vibrations also supports this ordering of the orbitals.The same orbital assignment has recently been proposed by Frost et al.⁵, using a comparison with the HCP photoelectron spectrum. The present paper supports their assignment of orbitals and (00⁰0)-(00⁰0) transitions. There are, however, some disagreements concerning the vibrational analysis. This is probably due to the fact that the HCN spectrum of Frost et al.⁵ revealed less structure than ours. As indicated by Figure 5 there is possibly still more structure to be revealed.     

III: PROPERTIES OF COMPLEX SYSTEMS

The molecular structures, vibrational frequencies, dissociation energies and electron affinities of the Br₂/Br^? ₂, Br₂O/Br₂O^?, Br₂O₂/Br₂O^? ₂, Br₂O₃/Br₂O^? ₃, and Br₂O₄/Br₂O^? ₄ systems have been investigated using density functional theory (DFT) and hybrid Hartree-Fock/density functional theory. The methods used have been carefully calibrated against a comprehensive tabulation of experimental electron affinities, (Rienstra-Kiracofe, J. C., Tschumper, G. S., Shaefer, H. F., Nandi, S. and Ellison, G. B., 2002, Chem. Rev., 102, 231). Four different types of neutral/anion energetic difference are reported in this work: the adiabatic electron affinity (EA_ad), the zero-point corrected EA_ad (EA_zero), the vertical electron affinity (EA_vert), and the vertical detachment energy (VDE). The basis set used in this work is of double-zeta plus polarization quality with additional s- and p-type diffuse functions, and is denoted as DZP⁺⁺. The BHLYP method does well in reproducing the very limited experimental energetics, while the B3LYP method does well for the few known vibrational frequencies. The final predicted electron affinities with the BHLYP method are 3.41 eV (Br, experiment 3.36 eV), 3.02 eV (Br₂, experiment 2.6 ± 0.2 eV), 3.27 eV (Br₂O), 2.93 eV (Br₂O₂), 3.07 eV (Br₂O₃), and 2.54 eV (Br₂O₄). The global minimum structures for several of the larger dibromine oxides and their anions are unusual. For neutral Br₂O₂ the peroxide structure (BrOOBr) lies lowest, but for the anion a loosely bound C_s symmetry BrO-BrO^? structure lies lowest for the hybrid functionals, while a C₂ symmetry peroxide BrOOBr^? structure lies lowest for the pure functionals. Furthermore, the C₂ structures are found to exhibit an inverse symmetry breaking problem, and should be interpreted with caution. For neutral Br₂O₃, a chain structure Br-O₃-Br lies lowest, while the complex Br···O₃···Br^? lies lowest for the negative ion. For neutral Br₂O₄, a chain structure Br-O₄-Br lies lowest, while the complex BrO^?···BrO₃ lies lowest for the negative ion.     

XPS-investigation of intramolecular charge transfer in polynitro-aminobenzenes

It has been shown that the shake-up energy ΔE¹, which depends on the ionization potential (IP) of the neutral (poly)nitro-aminobenzenes, vanishes for IP≈ 8.4 eV. The λ values, which measure the contribution of intramolecular charge-transfer configurations in the molecules-in-molecules models correlate rather well with the difference E_II- E₁, i.e., the difference of the peak positions corresponding to lower and higher binding energies.     

Effects of alkyl side chains on properties of aliphatic amino acids probed using quantum chemical calculations

Effects of alkyl side chains (R‐) on the electronic structural properties of aliphatic amino acids are investigated using quantum mechanical approaches. The carbon (C 1s) binding energy spectra of the aliphatic amino acids are derived from the C 1s spectrum of glycine (the parent spectrum) by the addition of spectral peaks, depending on the alkyl side chains, appearing in the lower energy region IP < 290 eV (where IP is the ionization potential). The two glycyl parent spectral peaks of the amide 291.0 eV [C₍₂₎] and carboxylic 293.5 eV [C₍₁₎] C atoms are shifted in the aliphatic amino acids owing to perturbations depending on the size and structure of the alkyl chains. The pattern of the N 1s and O 1s spectra in glycine is retained in the spectra of the other amino acids with small shifts to lower energy, again depending on the alkyl side chain. The Hirshfeld charge analyses confirm the observations. The alkyl effects on the valence binding energy spectra of the amino acids are concentrated in the middle valence energy region of 12–16 eV, and hence this energy region of 12–16 eV is considered as the `fingerprint' of the alkyl side chains. Selected valence orbitals, either inside or outside of the alkyl fingerprint region, are presented using both density distributions and orbital momentum distributions, in order to understand the chemical bonding of the amino acids. It is also observed that the HOMO–LUMO energy gaps of the aliphatic amino acids are reduced with the growth of the alkyl side chain.     

Anode plasma structure in a gas discharge with neutral density depleted by ionization

We consider the anode plasma structure in a gas discharge with density of neutral atoms (neutrals) depleted by strong ionization. We obtain analytical solutions of the quasi-neutrality equation for the potential distribution and a condition for the existence of anode plasma in the one-dimensional case for arbitrary potential dependences of the neutral depletion frequency and the electron density. We consider the special cases of a constant neutral depletion frequency, ionization by Maxwellian electrons, and ionization by an intense electron beam under the conditions of collisionless ion motion and Boltzmann thermal electron distribution. The solutions for the first two cases at zero depletion parameter, i.e., at constant gas density, match those obtained in [1] by a power series expansion. In the case of ionization by Maxwellian electrons, the formation of anode plasma at reasonable working-gas flow rates is shown to be possible only at a fairly high electron temperature (if, e.g., xenon is used as the working gas, then T _e ≥ 5 eV). Steady-state solutions of the quasi-neutrality equation under ionization by an intense electron beam exist only if the ratio of the electron beam density to the maximum thermal electron density does not exceed a certain limiting value.     

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.     

Electronic structure of selenium aggregates by a self-consistent method including 4d orbitals

The electronic structure of small selenium aggregates Se_{n >} (2 < n < 10) has been calculated using the CNDO method on a complete basis 4s, 4p, 4d. The energy per bond, the ionization potentials (IP) and the electronic affinities (EA) are given as a function of the aggregate size. The IP and EA converge to a common value which approaches the work function of bulk metal. The calculated gap is in good agreement with recent experimental determinations.     

Ab initio calculation of the first ionization potential in linear alkanes using exciton theory

An ab initio calculation is used to give the form of the ionization potential in the alkane series and to explain the origin of the various contributions to this potential. The question of whether the ionization relates to a σ-type orbital, composed mainly of carbon atomic orbitals, or to a π-type, composed of CH bonds, is considered. The results show a gradual evolution from a CH ionization (13·26 eV) in CH₄ to a CC ionization (10·0 eV) at the farthest limit of the series.     

Absolute double differential ionization cross-section for electron impact: He

Summary A complete set of absolute double differential cross-section (DDCS) for electron impact ionization of helium has been measured at an incident energyE ₀=500 eV. The angular distributions of the ejected and scattered electrons between 40 and 435.5 eV have been measured over the angular range of (10÷145)^o. This work supplements the mapping of DDCS for ejected electron energies close to (E ₀−IP)/2 (IP is the He 1s ionization energy), a region where the experimental data are fragmentary. The possibility of representing the full Bethe surface with a simple functional form is investigated. To speed up publication, the authors of this paper have agreed to not receive the proofs for correction.     

Electron affinities,molecular structures,and thermochemistry of the fluorine,chlorine and bromine substituted methyl radicals

Four independent density functional theory (DFT) methods have been employed to study the structures and electron affinities of the methyl and F-, CI- and Br-substituted methyl radicals and their anions. The methods used have been carefully calibrated against a comprehensive tabulation of experimental electron affinities (Chemical Reviews, 2002, 102, 231). The first dissociation energies together with the vibrational frequencies of these species are also reported. The basis sets used in this work are of double-ζ plus polarization quality with additional s- and p-type diffuse functions, labelled as DZP++. Previously observed trends in the prediction of bond lengths by the DFT methods are also demonstrated for the F-, Cl- and Br-substituted methyl radicals and their anions. Generally, the Hartree-Fock/DFT hybrid methods predict shorter and more reliable bond lengths than the pure DFT methods. Neutral-anion energy differences reported in this work are the adiabatic electron affinity (EA_ad), the vertical electron affinity (EA_vert), and the vertical detachment energy (VDE). Compared with the available experimental electron affinities, the BHLYP method predicts much lower values, while the other methods predict values (EA_ad, EA_vert, VDE) close to each other and almost within the experimental range. For those systems without reliable experimental measurements, our best adiabatic EAs predicted by BLYP are 0.78 (CHF₂), 1.23 (CHFCl), 1.44 (CHFBr), 1.61 (CHClBr), 2.24 (CF₂Cl), 2.42 (CF₂Br), 2.56 (CFBr₂), 2.36 (CCl₂Br), 2.46 (CClBr₂), and 2.44 eV (CFClBr). The most striking feature of these predictions is that they display an inverse relationship between halogen electronegativity and EA. The DZP++B3LYP method determines the vibrational frequencies in best agreement with available experimental results for this series, with an average relative error of ～2%. The value of using a variety of DFT methods is observed in that BHLYP does best for geometries, BLYP for electron affinities, and B3LYP for vibrational frequencies. These theoretical results serve to resolve several disagreements between competing experiments. Several other experiments appear to have drawn incorrect conclusions. For example, CHCl₂ is significantly pyramidal, unlike the experimental inferences, and clearly the experimental CCl₂—Cl dissociation energy is too large.