| 1. |
- Bao, Zhuo, et al.
(författare)
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Detailed Theoretical and Experimental Description of Normal Auger Decay in O2
- 2008
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Ingår i: Journal of Physics B. - : IOP Publishing. - 0953-4075 .- 1361-6455. ; 41:12, s. 125101-
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Tidskriftsartikel (refereegranskat)abstract
- The normal Auger electron spectrum of the O-2 molecule is assigned in detail on the basis of ab initio valence configuration interaction (CI) wavefunctions. Potential energy curves of the ground state, the core-ionized states and the doubly charged final states are calculated and Auger decay rates are obtained with the one-centre approximation. Using the lifetime vibrational interference method, band shapes are obtained for all contributions to the Auger spectrum. The calculated Auger electron spectrum allows us to identify all features observed experimentally. Significant differences to previous assignments are reported. A quantitative simulation of the spectrum is given on the basis of a curve-fitting procedure, in which the energetic positions and intensities of the theoretical bands were optimized. Besides providing a basis for a refined analysis of the spectrum, the fit allows us to assess the accuracy of the calculation. As expected for this level of theory, the absolute accuracy of the valence CI energies is found to be about 0.3 eV. The inherent error of the one-centre transition rates is less than 5% of the most intense transition in the spectrum. The frequently questioned one-centre Auger transition rates are shown to be rather appropriate if applied with reasonable wavefunctions and if the vibrational band structure of the molecular spectrum is properly taken into account.
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| 2. |
- Bao, Zhuo, 1977-
(författare)
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Synchrotron Radiation Studies of Free and Adsorbed Molecules
- 2008
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- This thesis contains two parts. The first part concerns the research work on free molecules using synchrotron-radiation-related techniques. Auger electron spectra of two free open-shell molecules, O2 and NO, were studied experimentally and theoretically. Photoionization experimental technique with tunable synchrotron radiation source was used to induce core-level electron ionization and obtain the KVV normal Auger electron spectra. A quantitative assignment of O2 normal Auger spectrum was obtained by applying ab initio CI calculations and LVI Auger line shape simulations including the bond length dependence of Auger transition rates. The photon energy dependence of normal Auger electron spectra was focused on with photon energies in the vicinities of core-ionization threshold energies. Consequently, the MAPCI (Molecular Auger Post Collision Interaction) theory was developed. Taking the near-threshold O2 normal Auger spectrum as an example, the two extreme cases of MAPCI effect, “atomic-like PCI” and “molecular PCI”, were discovered and discussed. The effect of shape resonance on near-threshold molecular normal Auger spectrum was discussed taking NO near threshold normal Auger spectra as example.The second part deals with research work on the chemisorption of small epoxy organic molecules, ethylene oxide, methyl oxirane, on Si (100) surfaces. Synchrotron radiation related techniques, UPS, XPS and NEXAFS, were applied. Based on the valence photoemission spectra, C 1s and Si 2p XPS spectra, the epoxy ring opening reactions of these molecules in chemisorption process were proved. Further tentative search for the surface-adsorbate CDAD effect was performed, and no evident circular dichroism was confirmed.
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| 3. |
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| 4. |
- Ceolin, Denis, et al.
(författare)
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Fragmentation of methyl chloride studied by partial positive and negative ion-yield spectroscopy
- 2007
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Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 126:8, s. 084309-
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Tidskriftsartikel (refereegranskat)abstract
- The authors present partial-ion-yield experiments on the methyl chloride molecule excited in the vicinity of the C12p and C1s inner shells. A large number of fragments, cations produced by dissociation or recombination processes, as well as anionic species, have been detected. Although the spectra exhibit different intensity distributions depending on the core-excited atom, general observations include strong site-selective fragmentation along the C-Cl bond axis and a strong intensity dependence of transitions involving Rydberg series on fragment size.
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| 5. |
- Feifel, Raimund, et al.
(författare)
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Probing the valence character of O-1s -> Rydberg excited O-2 by participator Auger decay measurements and partial ion yield spectroscopy following x-ray absorption
- 2007
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Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 126:17, s. 174304-
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Tidskriftsartikel (refereegranskat)abstract
- The valence character of O 1s -> Rydberg excited O-2 is investigated by means of participator Auger decay spectroscopy, performed at selected photon energies across the K-shell resonance region, and by means of partial ion yield x-ray absorption spectroscopy. For several of the excitation energies studied, the authors find substantial sigma(*)((4)Sigma(-)(u),(2)Sigma(-)(u)) valence character being mixed with ns sigma and np sigma ((4)Sigma(-)(u),(2)Sigma(-)(u)) Rydberg states. An experimental indication of a coupling between the channels associated with quartet and doublet ion cores is considered and discussed. New spectroscopic constants are derived for the singly ionized X (2)Pi(g) state of O-2 based on the observation of at least 20 vibrational sublevels.
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| 6. |
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| 7. |
- Fink, Reinhold, et al.
(författare)
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Specific production of very long-lived core-excited sulfur atoms by 2p(-1)sigma* excitation of the OCS molecule followed by ultrafast dissociation
- 2006
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Ingår i: Journal of Physics B. - 0953-4075 .- 1361-6455. ; 39:12, s. L269-L275
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Tidskriftsartikel (refereegranskat)abstract
- A core-excited sulfur state with a lifetime almost one order of magnitude longer than in molecular 2p core-hole states is selectively produced by ultrafast dissociation of S 2p -> sigma* excited OCS. Clear evidence for this is provided by strong atomic peaks (20% of the total intensity) in x-ray fluorescence but very weak ones (2%) in the corresponding resonant Auger spectrum. Corroborating the assignment of the spectra, ab initio calculations explain the enhanced lifetime: the Auger decay of the produced D-3(3) (2p(5)3p(5)) sulfur state is strongly decreased as it contradicts a newly derived propensity rule of the L2,3MM Auger decay.
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| 8. |
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| 9. |
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| 10. |
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| 11. |
- Piancastelli, Maria Novella, et al.
(författare)
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A High-resolution Study of Resonant Auger Decay Processes in N2O After Core Electron Excitation from Terminal Nitrogen, Central Nitrogen and Oxygen Atoms to the 3π LUMO
- 2007
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Ingår i: Journal of Physics B. - : IOP Publishing. - 0953-4075 .- 1361-6455. ; 40:17, s. 3357-3365
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Tidskriftsartikel (refereegranskat)abstract
- Decay spectra of N2O following excitation to the N terminal (Nt) → π*, N central (Nc) → π* and O is → π* intermediate states are reported. The final states reached after participator decay show resonant enhancement consistent with a local-density-of-states analysis based on the Mulliken population of the valence molecular orbitals. In particular, the X-state is resonantly enhanced mostly after excitation from the Nt 1s and the O Is core levels to the π*, while the B-state is mostly enhanced following the excitation of the Nc Is → π* intermediate state. Below the Nt Is threshold, the lowest lying peak related to spectator decay falls at lower binding energy than the highest lying participator peak. This can be attributed to a particularly strong screening effect exerted by the excited electron in the LUMO.
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| 12. |
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| 13. |
- Piancastelli, Maria Novella, et al.
(författare)
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Electronic and Geometric Structure of Methyl Oxirane Adsorbed on Si (100) 2 × 1
- 2007
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Ingår i: Applied Surface Science. - : Elsevier BV. - 0169-4332 .- 1873-5584. ; 254:1, s. 108-112
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Tidskriftsartikel (refereegranskat)abstract
- Electronic and geometric properties of the adsorbate–substrate complex formed upon adsorption of methyl oxirane on Si(1 0 0)2 × 1 at room temperature is reported, obtained with synchrotron radiation-induced valence and core-level photoemission. A ring-opening reaction is demonstrated to occur, followed by a five-membered ring formation involving two of the Si surface atoms bound to a surface dimer. Core-level photoemission spectra support the ring-opening reaction and the SiO and SiC bond formation, while from the valence spectra a more extended molecular fragmentation can be ruled out. We discuss the most likely geometry of the five-membered ring.
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| 14. |
- Piancastelli, Maria Novella, et al.
(författare)
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Electronic Structure of Core-excited and Core-ionized Methyl Oxirane
- 2007
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Ingår i: Journal of Electron Spectroscopy and Related Phenomena. - : Elsevier BV. - 0368-2048 .- 1873-2526. ; 156, s. 259-264
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Tidskriftsartikel (refereegranskat)abstract
- We report a detailed analysis of the electronic structure of methyl oxirane, including core-level photoelectron spectroscopy, X-ray absorption at both C and O K-shells, resonant Auger and normal Auger spectroscopy. The X-ray absorption spectra (XAS) around the C K-edge can be easily interpreted on the ground of the chemical shift between the carbon atoms with different chemical environments. The X-ray absorption data around the O K-edge are quite structureless, hinting for a likely fragmentation process (possibly implying a ring-opening reaction). In resonant Auger spectra obtained after excitation below both the C 1s and O 1s ionization thresholds we notice a predominance of spectator decay implying a strong mixing between empty molecular orbitals and Rydberg states.
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| 15. |
- Piancastelli, Maria Novella, et al.
(författare)
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Partial cation and anion-yield experiments in ammonia around the N 1s ionization threshold
- 2007
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Ingår i: Journal of Electron Spectroscopy and Related Phenomena. - : Elsevier BV. - 0368-2048 .- 1873-2526. ; 155:1-3, s. 86-90
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Tidskriftsartikel (refereegranskat)abstract
- We report partial cation and anion-yield measurements around the N K edge in isolated ammonia molecules. Due to the dominance of spectator electronic decay following Rydberg excitations, fragmentation was found to be more extensive following excitation to intermediate states of Rydberg character compared to excitation of states with molecular-orbital character. Unusual stability of the NH32+ fragment produced directly above threshold by normal-Auger decay is attributed to a stable planar geometry induced by a specific electronic configuration. Hydrogen anions are not detected above threshold except following the decay of resonant doubly excited neutral states embedded in the K-shell ionization continuum.
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| 16. |
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| 17. |
- Tanaka, T., et al.
(författare)
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Symmetry-resolved x-ray absorption fine structure and resonant Auger-spectator-electron decay study of O 1s→Rydberg resonances in O2
- 2008
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Ingår i: Physical Review A. Atomic, Molecular, and Optical Physics. - 1050-2947 .- 1094-1622. ; 78:2, s. 022516-
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Tidskriftsartikel (refereegranskat)abstract
- A series of resonant Auger-electron spectra excited at selected photon energies across the O 1s -> Rydberg resonances in O-2 has been measured. Applying a spectator-electron shake relaxation model originally introduced for atomic resonant Auger-electron spectra, and using, to a large extent, the assignments for the core-excited resonances available from the literature, many of the observed spectator Auger-electron final states are assigned in terms of cationic Rydberg series. Vice versa the resonant Auger-electron spectra are used for consistency tests of the literature assignments for the core-excited intermediate Rydberg states. For some of the latter, alternative assignments are proposed for reasons discussed.
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| 18. |
- Travnikova, Oksana, et al.
(författare)
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A Study of Substituent Effects for Aliphatic CH3-X Compounds by Resonant Auger Spectroscopy
- 2009
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 11:5, s. 826-833
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Tidskriftsartikel (refereegranskat)abstract
- In this study linear free energy relationships (LFER) are applied to the relaxation of core-excited states in aliphatic CH3X compounds. There are at least two valence orbitals involved in Auger decay following CCH31s →σ*C–X excitation, which may as well be localized on the substituents in this series. Therefore, the observed property cannot be strictly attached to the so-called reaction center. The behavior of substituent constants in the description of core-hole processes in aliphatic compounds is also checked on C1s ionization potentials for the extended series of substituted methanes. The role of the inductive effect for both resonant Auger kinetic energies (Ek) and C1s binding energies (Ecoreb) is very important. CCH31s →σ*C–X excitation energies do not show any significant correlations with inductive substituent constants. On the contrary, Taft’s inductive parameters alone give good correlations for Ek. A simple model with ‘Z + 1’ approximation is developed to describe Ek and explain the observed correlations:Ek = Ecoreb− (Ev(Z)b + Eea(Z+1)+),where Ebv(Z) is the valence ionization potential for CH3X and Eea(Z+1)+ is the electron affinity for [NH3X]+.
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| 19. |
- Travnikova, Oksana, et al.
(författare)
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Assignment of the L2,3VV normal Auger decay spectrum of Cl-2 by ab initio calculations
- 2009
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Ingår i: Chemical Physics Letters. - : Elsevier BV. - 0009-2614 .- 1873-4448. ; 474:1-3, s. 67-73
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Tidskriftsartikel (refereegranskat)abstract
- Auger decay processes of the Cl 2p ionized states have been studied in Cl-2 by means of high- resolution electron spectroscopy and ab initio calculations. This led to reassignment of the normal L2,3VV Auger decay spectrum of Cl2. The reliability of this assignment is strongly supported by an independent measurement of the L2; 3VV Auger electron spectrum of Cl2 which has been obtained after selective Cl 2p(3/2)(-1) photoionization of the chlorine molecule. Partial Auger transition rates for the three nongenerate spin-orbit and molecular- field- split 2p(-1) states - 2p(3/2,3/2)(-1) ((2)Pi(3/2)), 2p(3/2,1/2)(-1)((2)Sigma(+)(1/2)) and 2p(1/2,1/2)(-1)((2)Pi(1/2)) - show differences similar to the ones reported in previous works for HCl.
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| 20. |
- Travnikova, Oksana, et al.
(författare)
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Disentangling the complex line profiles in the Cl 2p photoelectron spectra of Cl-2
- 2006
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Ingår i: Chemical Physics Letters. - : Elsevier BV. - 0009-2614 .- 1873-4448. ; 426:4-6, s. 452-458
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Tidskriftsartikel (refereegranskat)abstract
- High-resolution Cl (2p) photoelectron spectra Of Cl-2 are reported and their complex structure is analyzed in detail, taking into account molecular field (NIF), spin-orbit (SO) and parity splitting. High-level ab initio calculations were performed to provide reliable values for spectroscopic parameters. Accurate data analysis enabled us to determine the value of molecular-field splitting of 86 7 meV, and values of 92 5, 79 11 and 105 12 meV for the lifetime line widths of the (2)Pi(1/2), (2)Sigma(+)(1/2) and (2)Pi(3/2) states, respectively. The gerade-ungerade splitting of less than 5 meV is obtained from the calculations.
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| 21. |
- Travnikova, Oksana, 1981-
(författare)
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Structure and Dynamics of Core-Excited Species
- 2008
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- In this thesis we have performed core-electron spectroscopy studies of gas phase molecular systems starting with smaller diatomic, continuing with triatomic and extending our research to more complex polyatomic ones. We can subdivide the results presented here into two categories: the first one focusing on electronic fine structure and effect of the chemical bonds on molecular core-levels and the other one dealing with nuclear dynamics induced by creation of a core hole. In our research we have mostly used synchrotron radiation based techniques such as X-ray Photoelectron (XPS), X-ray Absorption (XAS), normal and Resonant Auger (AES and RAS, respectively) and Energy-Selected Auger Electron PhotoIon COincidence (ES-AEPICO) spectroscopies.We have demonstrated that resonant Auger spectroscopy can be used to aid interpretation of the features observed in XAS for Rydberg structures in the case of Cl2 and C1s−1π*1 states of allene molecules. The combined use of high-resolution spectroscopy with ab initio calculations can help the interpretation of strongly overlapped spectral features and disentangle their complex profiles. This approach enabled us to determine the differences in the lifetimes for core-hole 2p sublevels of Cl2 which are caused by the presence of the chemical bond. We have shown that contribution in terms of the Mulliken population of valence molecular orbitals is a determining factor for resonant enhancement of different final states and fragmentation patterns reached after resonant Auger decays in N2O.We have also performed a systematic study of the dependence of the C1s resonant Auger kinetic energies on the presence of different substituents in CH3X compounds. For the first time we have studied possible isomerization reaction induced by core excitation of acetylacetone. We could observe a new spectral feature in the resonant Auger decay spectra which we interpreted as a signature of core-excitation-induced keto-enol tautomerism.
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