Final State Relaxation Research Articles

Unexpected XPS Binding Energy Observations Further Highlighted by DFT Calculations of Ruthenocene-Containing [IrIII(ppy)2(RCOCHCORc)] Complexes: Cytotoxicity and Crystal Structure of [Ir(ppy)2(FcCOCHCORc)

The series of iridium(III) complexes, [Ir(ppy)2(RCOCHCOR')], with R = CH3 and R' = CH3 (1), Rc (2), and Fc (3), as well as R = Rc and R' = Rc (4) or Fc (5), and R = R' = Fc (6), ppy = 2-phenylpyridinyl, Fc = FeII(η5-C5H4)(η5-C5H5), and Rc = RuII(η5-C5H4)(η5-C5H5), has been investigated by single-crystal X-ray crystallography and X-ray photoelectron spectroscopy (XPS) supplemented by DFT calculations. Here, in the range of 3.74 ≤ ΣχR ≤ 4.68, for Ir 4f, Ru 3d and 3p and N 1s orbitals, binding energies unexpectedly decreased with increasing ΣχR (ΣχR = the sum of Gordy group electronegativities of the R groups on β-diketonato ligands = a measure of electron density on atoms), while in Fe 2p orbitals, XPS binding energy, as expected, increased with increasing ΣχR. Which trend direction prevails is a function of main quantum level, n = 1, 2, 3…, sub-quantum level (s, p, d, and f), initial state energies, and final state relaxation energies, and it may differ from compound series to compound series. Relations between DFT-calculated orbital energies and ΣχR followed opposite trend directions than binding energy/ΣχR trends. X-ray-induced decomposition of compounds was observed. The results confirmed good communication between molecular fragments. Lower binding energies of both the Ir 4f7/2 and N 1s photoelectron lines are associated with shorter Ir-N bond lengths. Cytotoxic tests showed that 1 (IC50 = 25.1 μM) and 3 (IC50 = 37.8 μM) are less cytotoxic against HeLa cells than cisplatin (IC50 = 1.1 μM), but more cytotoxic than the free β-diketone FcCOCH2COCH3 (IC50 = 66.6 μM).

New-Generation Electron-Propagator Methods for Molecular Electron-Binding Energies.

A new generation of electron-propagator methods for the calculation of electron binding energies has surpassed its antecedents with respect to accuracy, efficiency, and interpretability. No adjustable parameters are introduced in these fully ab initio procedures. Numerical tests versus several databases of valence, vertical electron binding energies of closed-shell molecules and atoms have been performed. Easily interpreted self-energy approximations with cubic arithmetic scaling produce mean absolute errors (MAEs) of 0.2 and 0.3 eV for electron detachments and attachments, respectively. The most accurate explicitly renormalized methods with fifth-power arithmetic scaling yield MAEs below 0.1 eV for detachments and attachments. Approximate renormalization leads to more efficient fifth-power alternatives for electron detachments that achieve similar accuracy with fewer bottleneck operations. Composite protocols generate excellent predictions versus highly accurate basis-extrapolated standards and experiments. The validity of the diagonal self-energy approximation and the accuracy of the approximate renormalizations are confirmed. The success of these perturbative methods based on canonical Hartree-Fock orbitals rests on a Hermitized, intermediately normalized superoperator metric. The results of all of the new-generation calculations may be analyzed in terms of final-state orbital relaxation and differential correlation effects.

Electronic structure and intramolecular interactions in three methoxyphenol isomers.

Electronic structures and intramolecular interactions of three methoxyphenol positional isomers and their rotamers have been studied using core X-ray photoelectron spectroscopy and quantum mechanical calculations. The structural calculations are benchmarked against published calculations of enthalpy of formation and rotational constants, and published experimental data. The good agreement obtained confirms the accuracy of the results. A single rotamer of each isomer was then selected and the C 1s photoelectron spectra calculated and compared with experiment. Good agreement is obtained, and the calculations were extended to investigate the effects of conformation. For 3-methoxyphenol, the difference in the C 1s binding energy of the conformers is small, <0.15 eV. For 2-methoxyphenol, whose ground state includes an OH⋯OCH3 hydrogen bond, the higher energy rotamers show the largest shifts for the methyl carbon atom, whereas the ring carbon bonded to OH hardly shifts The theoretical differences in core level energies of the two rotamers of 4-MP are still smaller, <0.05 eV. By comparing calculations neglecting or including final state relaxation upon ionization, the relaxation energy of the phenyl carbons in all isomers is found to be ∼0.5 eV, while that of the methyl groups is ∼1.3 eV.

Electron Propagator Methods for Vertical Electron Detachment Energies of Anions: Benchmarks and Case Studies.

Ab initio electron propagator methods are efficient and accurate means of calculating vertical electron detachment energies of closed-shell, molecular anions with nuclei from the first three periods. Basis set extrapolations enable definitive comparisons between electron propagator results and benchmarks defined by total energy differences obtained with coupled-cluster, single, double, plus perturbative triple substitution theory. The best compromises of accuracy and efficiency are provided by the renormalized, partial third-order, diagonal (P3+) self-energy and by the nondiagonal, renormalized, second-order (NR2) approximation. The outer-valence Green function, the two-particle-one-hole Tamm-Dancoff approximation, the third-order algebraic diagrammatic construction, and the renormalized third-order methods also are examined. A detailed analysis of errors for small anions is performed. Case studies include F-(H2O) and Cl-(H2O) complexes, C5H5-, two P2N3- pentagonal rings, and a superhalide, Al(BO2)4-, whose electron detachment energy is more than double those of the halide anions. These applications illustrate the versatility of electron propagator methods, their utility for interpreting negative-ion photoelectron spectra, and their promise in the discovery of unusual properties and patterns of chemical bonding. Composite methods, which combine basis set effects calculated at the relatively efficient diagonal, second-order level and higher correlation effects calculated with small basis sets, provide excellent estimates of basis set-extrapolated P3+ or NR2 results and facilitate applications to large molecules. In the P3+ and NR2 methods, a judicious choice of low-order couplings between hole operators that correspond to the assumptions of Koopmans's theorem and operators that describe final-state relaxation and polarization and initial-state correlation leads to predictive accuracy, computational efficiency, and interpretive lucidity.

Core-level binding energy shifts as a tool to study surface processes on LaAlO3/SrTiO3

X-ray photoelectron spectroscopy (XPS) is used to study the adsorbed species on LalAlO3/SrTiO3 surfaces combined with computational modeling. Core level binding energy shifts are calculated from first-principles for various terminations of LaAlO3 (LAO) surfaces with adsorbed H and OH in different concentrations and with or without the presence of oxygen vacancies on the surface. Final state relaxation effects in the presence of the core hole are included. Energies of formation and adsorption for the various species and relevant reaction energies are calculated. These are used to interpret the changes in XPS spectra of an LAO film under different growth and annealing treatments. We find a peak with 2eV binding energy shift toward higher binding energy in the O1s spectrum cannot be associated with OH as is commonly assumed. Instead it is assigned to carbonaceous species by studying the corresponding changes in the C1s spectrum. The OH and H species are found to be too strongly bound to be removed at 500°C.

Electron propagators based on generalised density operators

ABSTRACTElectron binding energies and Dyson orbitals may be obtained from the poles and residues of the electron propagator. The Dyson quasiparticle equation provides a convenient route to computing this information. Systematic approximations to the latter equation's self-energy, wherein electron correlation and final-state orbital relaxation are described, may be expressed in terms of the elements of the superoperator Hamiltonian matrix. Perturbative methods of electron propagator theory in wide use are based on a reference determinant constructed with canonical, Hartree–Fock orbitals. Generalised matrix elements of the superoperator Hamiltonian that accommodate non-integer occupation numbers associated with general, orthogonal spin orbitals are presented for the first time. Non-Hermitian terms may be systematically eliminated with perturbative corrections to generalised reference density operators. The structure of self-energy approximations that are complete through second, third, fourth or fifth order is presented in terms of superoperator Hamiltonian matrix elements. The present extensions pertain when generalised, zeroth-order density operators expressed in terms of orthonormal spin orbitals are employed.

Study of metal specific interaction, F-LUMO and VL shift to understand interface of CuPc thin films and noble metal surfaces

The performances of organic electronic devices are significantly associated with their energy level alignment at organic semiconductor/metal–electrode interfaces. The electronic character of an organic semiconducting molecular over-layer on a metal surface can vary from semiconducting to metallic, depending on the nature of the molecular orbitals with respect to the Fermi level of the electrode. The general tendency of extrapolating established models for single crystal substrates to ‘real’ device substrates is highly misleading. Hence, the importance of metal specific interaction, former lowest unoccupied molecular orbital (F-LUMO) and vacuum level (VL) shift have been investigated as a function of thickness of the deposited films by means of photoelectron spectroscopy (XPS and UPS) to understand the interface between CuPc and Cu, Ag, Pt and Au foils sequentially. The XPS data provides the signature of affectability of pyrrole sites of CuPc molecules for partial charge transfer from Cu and Ag substrates while a negligible effect on pyrrole cites resulted for Pt and Au substrates. Furthermore, the appearance of F-LUMO, a hybridized state close to the Fermi level gives confirmatory information about partial charge transfer. Contrary to the general belief that vacuum level shift caused by charge transfer can partially or totally cancel that for push back effect, our observation indicates that the partial charge transfer does not play significant role in the shift of vacuum level. The entire thickness dependent electronic energy level alignment of CuPc films on all noble metal substrates is explained in terms of a combined effect of partial charge transfer and photoemission final state relaxation energy. A systematic variation of HOMO-FWHM was observed with CuPc thickness due to continuous change in molecular orientation.

Core-level photoemission from nanocluster-matrix composites: Au clusters in amorphous carbon

Abstract We investigate a system consisting of Au nano-clusters and amorphous carbon (a-C) via core-level photoemission. While the ability of photoemission to characterize nano-sized metal clusters is well-known, still some issues deserve investigation. For example, the well-established dominance of final-state relaxation effects in core-level spectra from nano-clusters necessarily involves a crucial role of the cluster dielectric-environment. To the best of our knowledge however, a thorough discussion on this point is lacking. We thus intend to investigate dielectric-environment effects by considering several configurations for Au clusters, i.e. supported and embedded, with the latter obtained either by depositing a-C on top of supported clusters or by co-depositing a-C and Au. We analyze the Au4 f spectrum from clusters accounting for both cluster size and cluster location with respect to the a-C matrix. We show that spectral changes caused by a-C deposition are entirely explained in terms of changes in the cluster dielectric environment. Moreover, we prove that supported clusters are in a well-characterized dielectric environment, while embedded clusters are not. This is because embedded clusters, whatever the method of production, are spatially distributed over the matrix surface-region which is characterized by rapid fluctuations in the dielectric constant.

Understanding surface core-level shifts using the Auger parameter: A study of Pd atoms adsorbed on ultrathin SiO2films

Auger parameter (\ensuremath{\Delta}\ensuremath{\alpha}) measurements have been employed to determine the extent to which initial- and final-state effects govern surface core-level shifts in x-ray photoelectron spectroscopy (XPS) measurements of Pd atoms confined between a bilayer SiO${}_{2}$ film and its Ru(0001) support. For atoms bound in this manner, we note negative binding energy shifts (\ensuremath{\Delta}BEs) of \ensuremath{\sim}0.3 eV, relative to the Pd 3$d$ peak position in the bulk, and attribute these shifts to large variations in the initial-state orbital energies of the supported atoms (\ensuremath{\sim}1.1 eV towards ${E}_{F}$), coupled with decreased final-state relaxation contributions (\ensuremath{\sim}0.8 eV). Theoretical calculations reveal that, despite small partial positive charges and decreased final-state screening, the decreased 4$d$-5sp hybridization of the undercoordinated Pd atoms results in large enough upward 3$d$ orbital-energy shifts to yield the net-negative \ensuremath{\Delta}BE noted by XPS.

Positive XPS binding energy shift of supported CuN-clusters governed by initial state effects

An initial state effect is established as origin for the positive 2p core electron binding energy shift found for CuN-clusters supported by a thin silica layer of a p-doped Si(100) wafer. Using the concept of the Auger parameter and taking into account the usually neglected Coulomb correlation shift in the Auger final state (M4,5M4,5) it is shown that the initial state shift is comparable to the measured XPS shift while the final state relaxation shift contributes only marginally to the binding energy shift. The cluster results differ from the negative surface core-level shift of crystalline copper which has been explained in terms of a final state relaxation effect.

Thickness dependent electronic structure and morphology of rubrene thin films on metal, semiconductor, and dielectric substrates

The evolution of the electronic structure and morphology of rubrene thin films on noble-metal, semiconductor and dielectric substrates have been investigated as a function of thickness of deposited films by using photoelectron spectroscopy and atomic force microscopy. The clean polycrystalline Au and Ag were used as noble-metals, whereas, H passivated and SiO2 coated Si (100) were used as semiconductors and dielectric substrates. Discussion and comparison on interface dipole, energy level alignment, and surface morphology for the four cases are presented. The formation of dipole at metallic interfaces is found to occur due to push back effect. S parameter obtained from the variation of barrier height with the change of work function of the contacting metal indicates moderately weak interaction between rubrene and the metal substrates. The thickness dependent energy level alignment of the physisorbed rubrene films on different substrates is explained by a dielectric model in terms of electrostatic screening of photo-holes or photoemission final state relaxation energy. Films on all the substrates are found to grow following Stranski−Krastnov type growth mode and are more ordered at higher coverage.

Photoemission and density functional theory study of Ge(100): Clean surface and Yb-induced (2×4) reconstruction

Clean and metal-adsorbed (100) surfaces of group-IV semiconductors, such as Si and Ge, often exhibit electronically and structurally similar reconstructions. However, the fundamental bulk properties of group-IV materials can have an impact on particular features of such systems, which are related, e.g., to final-state relaxation in photoemission and thus determine their spectral line shape. Here we have studied Yb/Ge(100)(2×4) reconstruction as well as clean Ge(100) surface by high-resolution photoelectron spectroscopy and ab initio calculations. An atomic geometry of both surfaces is thoroughly investigated. A detailed analysis of Ge 3d core-level photoemission, atomic origins of surface-shifted components, and final-state screening effects is presented. In particular, it is demonstrated that the core-hole screening plays an essential role in Ge 3d measurements, and that its amount in the complete screening model correlates well with the core-level binding energy of respective Ge atoms in the initial state. The results are discussed in the proper context of related reconstructions on Si(100).

The role of the Auger parameter in XPS studies of nickel metal, halides and oxides

The critical role of the Auger parameter in providing insight into both initial state and final state factors affecting measured XPS binding energies is illustrated by analysis of Ni 2p(3/2) and L(3)M(45)M(45) peaks as well as the Auger parameters of nickel alloys, halides, oxide, hydroxide and oxy-hydroxide. Analyses of the metal and alloys are consistent with other works, showing that final state relaxation shifts, ΔR, are determined predominantly by changes in the d electron population and are insensitive to inter-atomic charge transfer. The nickel halide Auger parameters are dominated by initial state effects, Δε, with increasing positive charge on the core nickel ion induced by increasing electronegativity of the ligands. This effect is much greater than the final state shifts; however, the degree of covalency is reflected in the Wagner plot where the more polarizable iodide and bromide have greater ΔR. The initial state shift for NiO is much smaller than those of Ni(OH)(2) or NiOOH and the effective oxidation state is much less than that inferred from the average electronegativity of the ligand(s). Auger parameter analysis indicates that the bonding in NiO appears to have stronger contributions from initial state charge transfer from the oxygen ligands than that in the hydroxide and oxyhydroxide consistent with the considerable differences in the Ni-O bond lengths in these compounds with some relaxation of this state occurring during final state phenomena. The Auger parameter of NiOOH is, however, shifted positively, like the iodide, indicating greater polarizability of the ligands and covalency in this bonding. There is support for more direct use of relative bond lengths in interpreting differences between related compounds rather than more general electronegativity or similar parameters.

XANES and XPS investigations of the local structure and final-state effects in amorphous metal silicates: (ZrO2)x(TiO2)y(SiO2)1−x−y

Amorphous quaternary [(ZrO(2))(x)(TiO(2))(y)(SiO(2))(1-x-y)] and ternary [(ZrO(2))(x)(SiO(2))(1-x)] silicates were synthesized using a sol-gel method and examined via XPS and XANES. Metal silicates are important industrial materials, though structural characterization is complicated because of their amorphous nature. Hard (Ti K- and Zr K-edge) and soft (Ti L(2,3)-edge) X-ray XANES spectra suggest the Ti and Zr coordination numbers in the quaternary silicates remain constant as the metal identity or total metal content (x, y, or x + y in the chemical formula) is varied. XPS core-line spectra from the quaternary silicates show large decreases in Ti 2p(3/2), Zr 3d(5/2), Si 2p(3/2), and O 1s binding energies due to increasing final-state relaxation with greater next-nearest neighbour substitution of Si for less-electronegative Ti/Zr, which was confirmed by analysis of the O Auger parameter. These decreases in binding energy occur without any changes in the ground-state energies (e.g., oxidation state) of these atoms, as examined by Ti L(2,3)-edge, Si L(2,3)-edge, and O K-edge XANES. Because most spectroscopic investigations are concerned with ground-state properties, knowledge of the contributions from final-state effects is important to understand the spectra from materials of interest.

XANES and XPS investigations of (TiO2)x(SiO2)1−x: the contribution of final-state relaxation to shifts in absorption and binding energies

The (TiO2)x(SiO2)1−x system (0 ≤ x ≤ 0.33) was synthesized by the sol–gel method and investigated by X-ray absorption near-edge spectroscopy (XANES) and X-ray photoelectron spectroscopy (XPS). The use of both hard (Ti K-edge) and soft (Ti L-edge) X-rays provides a useful way to monitor changes in the bulk and surface, respectively, of these amorphous materials. The average CN of both bulk-Ti and surface-Ti increases with greater x in the chemical formula, due to the larger ionic radius of Ti. Comparison of Ti K- and L-edge spectra of annealed samples revealed that Ti atoms at the surface have a higher average CN than in the bulk, likely due to the presence of surface hydroxide and water groups that can coordinate to the Ti centres. The O K-edge, Ti L-edge, and Si L-edge XANES absorption energies showed little to no change with Ti content, while the O 1s, Ti 2p, and Si 2p XPS BEs were found to decrease with increasing Ti content due to nearest-neighbour and next-nearest-neighbour effects, which lead to increased final-state relaxation. The degree of final-state relaxation is more significant than previously believed for these amorphous powders.

Coordination-Induced Shifts of Absorption and Binding Energies in the SrFe1−xZnxO3−δ System

The SrFe1−xZnxO3−δ system (0 ≤ x ≤ 1) was synthesized and investigated by X-ray absorption near-edge spectroscopy (XANES) and X-ray photoelectron spectroscopy (XPS). These techniques were used to examine the effect of substitution on metal charge and coordination number (CN) and to study the influence of ground-state and final-state effects on spectral energies. As x increases, a greater oxygen deficiency lowers the transition-metal CN, as observed by examination of Fe K- and Zn K-edge XANES spectra. Substitution of Fe by Zn results in shifts in the (Fe 2p and Zn 2p) XPS binding energies and (Fe and Zn) K-edge XANES absorption energies that are much greater than the shifts observed in the corresponding Fe L- and Zn L-edge XANES absorption energies. These shifts are due to increasing final-state relaxation with decreasing metal CN. The O K-edge XANES absorption energies and O 1s binding energies were found to shift in a similar fashion because of ground-state effects owing to a greater screening of the O n...

Effect of electrostatic screening on apparent shifts in photoemission spectra near metal/organic interfaces

Photoemission spectra of very thin organic films differ from that of thicker bulklike films. In particular, the binding-energy shifts in molecular orbitals at metal/organic interfaces vary as a function of the organic overlayer thickness. Using a simple image-charge model it is found that electrostatic screening can have a significant effect on the final-state relaxation energy. Good agreement between experimental results and theoretical calculations for a variety of dielectric substrates indicate that reported thickness dependent energy-level shifts in organic overlayer spectra can be accounted for by electrostatic screening. Models of organic interfaces based on photoemission spectra of organic thin films should therefore be re-examined.

Evaluation of the donor ability of phenanthrolines in iridium complexes by means of synchrotron radiation photoemission spectroscopy and DFT calculations

Synchrotron radiation XPS measurements of Ir 4f, N 1s and I 4d core levels for the compounds Ir(cod)(N-N)X (cod=1,5-cyclooctadiene; N-N=1,10-phenanthroline and substituted derivatives; X=Cl, I) are reported. The compounds Ir(cod)(3,4,7,8-Me4phen)X (3,4,7,8-Me4phen=3,4,7,8-tetramethyl-1,10-phenanthroline) were structurally characterized by single crystal X-ray analyses. The comparison among the binding energies shows differences that are interpreted in terms of electron density variations due to the change of the phenanthroline substituents. Such analysis provides a quantitative evaluation of the ligand donor properties. The trend in the measured binding energies is confirmed by the results obtained by DFT DeltaSCF calculations, which include final state relaxation effects, while the specific role of initial state effects has been assessed in terms of the Kohn-Sham eigenvalues analysis.

Core‐level shifts in complex metallic systems from first principle

AbstractWe show that core‐level binding energy shifts (CLS) can be reliably calculated within density functional theory. The scheme includes both the initial (electron energy eigenvalue) as well as final state (relaxation due to core‐hole screening) effects in the same framework. The results include CLS as a function of composition in substitutional random bulk and surface alloys. Sensitivity of the CLS to the local chemical environment in the bulk and at the surface is demonstrated. A possibility to use the CLS for structural determination is discussed. Finally, an extension of the model is made for Auger kinetic energy shift calculations. (© 2006 WILEY‐VCH Verlag GmbH &amp; Co. KGaA, Weinheim)

Spectroscopic analysis of small organic molecules: A comprehensive near-edge x-ray-absorption fine-structure study of C6-ring-containing molecules

We report high-resolution C 1s near-edge x-ray-absorption fine-structure (NEXAFS) spectra of the C6-ring-containing molecules benzene (C6H6), 1,3- and 1,4-cyclohexadiene (C6H8), cyclohexene (C6H10), cyclohexane (C6H12), styrene (C8H8), and ethylbenzene (C8H10) which allow us to examine the gradual development of delocalization of the corresponding pi electron systems. Due to the high experimental resolution, vibrational progressions can be partly resolved in the spectra. The experimental spectra are compared with theoretical NEXAFS spectra obtained from density-functional theory calculations where electronic final-state relaxation is accounted for. The comparison yields very good agreement between theoretical spectra and experimental results. In all cases, the spectra can be described by excitations to pi*- and sigma*-type final-state orbitals with valence character, while final-state orbitals of Rydberg character make only minor contributions. The lowest C 1s-->1pi* excitation energy is found to agree in the (experimental and theoretical) spectra of all molecules except for 1,3-cyclohexadiene (C6H8) where an energy smaller by about 0.6 eV is obtained. The theoretical analysis can explain this result by different binding properties of this molecule compared to the others.