| 1. |
- Bournel, F., et al.
(författare)
-
2-Butyne on Si(001) at room temperature: An XPS and NEXAFS study
- 2011
-
Ingår i: Journal of Electron Spectroscopy and Related Phenomena. - : Elsevier BV. - 0368-2048. ; 184:3-6, s. 323-326
-
Tidskriftsartikel (refereegranskat)abstract
- We present here a study of the adsorption of 2-butyne (CH3-C equivalent to C-CH3) on the Si(0 01)-2 x 1 silicon surface at room temperature using synchrotron radiation photoemission spectroscopy (XPS) and X-ray absorption spectroscopy (NEXAFS). In particular, the Si2p and C1s core levels were followed by real-time photoemission (measuring while dosing). The intensity of the Si2p surface state component gradually diminishes with an increasing exposure to the gas. The C1s photoemission line is decomposed into two main components with their vibrational series, attributed to the two inner carbons (bonded to silicon) and the two methyl carbons (protruding into the vacuum), respectively. C1s real-time XPS indicates that the chemical bonding of the molecule does not change from low coverage to saturation coverage. NEXAFS spectroscopy performed at the C K-edge using linearly polarized radiation reveals the presence of a pi*(C=C) molecular orbital parallel to the surface, resulting from the opening of the triple C equivalent to C bond and the formation of two sigma(Si-C) bonds. The attachment of the molecule via C-H bond scission (conserving the CC bond) is excluded. The clear-cut observation of a C=C bond, combined to our preceding angle-resolved UV photoemission spectroscopy (ARUPS) work [Bournel et al., Surf. Sci. 601 (2007) 3750] favors the on-dimer adsorption model at saturation (similar to 3 L). (C) 2010 Elsevier B.V. All rights reserved.
|
|
| 2. |
- Kunnus, K., et al.
(författare)
-
Identification of the dominant photochemical pathways and mechanistic insights to the ultrafast ligand exchange of Fe(CO)(5) to Fe(CO)(4)EtOH
- 2016
-
Ingår i: Structural Dynamics. - : AIP Publishing. - 2329-7778. ; 3:4
-
Tidskriftsartikel (refereegranskat)abstract
- We utilized femtosecond time-resolved resonant inelastic X-ray scattering and ab initio theory to study the transient electronic structure and the photoinduced molecular dynamics of a model metal carbonyl photocatalyst Fe(CO)(5) in ethanol solution. We propose mechanistic explanation for the parallel ultrafast intra-molecular spin crossover and ligation of the Fe(CO)(4) which are observed following a charge transfer photoexcitation of Fe(CO)(5) as reported in our previous study [ Wernet et al., Nature 520, 78 (2015)]. We find that branching of the reaction pathway likely happens in the (1)A(1) state of Fe(CO)(4). A sub-picosecond time constant of the spin crossover from B-1(2) to B-3(2) is rationalized by the proposed B-1(2) -> (1)A(1) -> B-3(2) mechanism. Ultrafast ligation of the B-1(2) Fe(CO)(4) state is significantly faster than the spin-forbidden and diffusion limited ligation process occurring from the B-3(2) Fe(CO)(4) ground state that has been observed in the previous studies. We propose that the ultrafast ligation occurs via B-1(2) -> (1)A(1) -> (1)A'Fe(CO)(4)EtOH pathway and the time scale of the (1)A(1) Fe(CO)(4) state ligation is governed by the solute-solvent collision frequency. Our study emphasizes the importance of understanding the interaction of molecular excited states with the surrounding environment to explain the relaxation pathways of photoexcited metal carbonyls in solution.
|
|
| 3. |
- Mathieu, C., et al.
(författare)
-
Nitrogen 1s NEXAFS and XPS spectroscopy of NH3-saturated Si(001)-2x1: Theoretical predictions and experimental observations at 300 K
- 2009
-
Ingår i: Physical Review B (Condensed Matter and Materials Physics). - 1098-0121. ; 79:20
-
Tidskriftsartikel (refereegranskat)abstract
- In the light of hybrid functional density-functional theory calculations of the core-excited and core-ionized states, this paper discusses original N 1s x-ray photoemission spectroscopy (XPS) and near-edge x-ray absorption fine-structure (NEXAFS) experimental data on the single-domain (vicinal) Si(001)-2x1 surface saturated by NH3 at 300 K. The theoretical approach enables to discuss the vibrational shape of the N 1s XPS spectrum and quantifies the binding-energy splitting due to intrarow and inter-row hydrogen bondings between amine pairs. The observed N 1s NEXAFS peaks are interpreted through the analysis of the contour maps of the antibonding Kohn-Sham orbitals of the NH2 adsorbate and through the Delta Kohn-Sham calculation of the transition energies, laying a theoretical basis for a discussion of the adsorbate spatial orientation. Finally, suggestions are given for future directions of research to get a further knowledge of a system that has potential applications as a template for molecular layer deposition and supramolecular assembly.
|
|
| 4. |
|
|
| 5. |
|
|
| 6. |
- Wernet, Philippe, 1971-, et al.
(författare)
-
Orbital-specific mapping of the ligand exchange dynamics of Fe(CO)5 in solution
- 2015
-
Ingår i: Nature. - : Springer Science and Business Media LLC. - 0028-0836 .- 1476-4687. ; 520:7545, s. 78-81
-
Tidskriftsartikel (refereegranskat)abstract
- Transition-metal complexes have long attracted interest for fundamental chemical reactivity studies and possible use in solar energy conversion. Electronic excitation, ligand loss from the metal centre, or a combination of both, creates changes in charge and spin density at the metal site that need to be controlled to optimize complexes for photocatalytic hydrogen production and selective carbon-hydrogen bond activation. An understanding at the molecular level of how transition-metal complexes catalyse reactions, and in particular of the role of the short-lived and reactive intermediate states involved, will be critical for such optimization. However, suitable methods for detailed characterization of electronic excited states have been lacking. Here we show, with the use of X-ray laser-based femtosecond resolution spectroscopy and advanced quantum chemical theory to probe the reaction dynamics of the benchmark transition-metal complex Fe(CO)5 insolution, that the photoinduced removal of CO generates the 16-electron Fe(CO)4 species, a homogeneous catalyst with an electron deficiency at the Fe centre, in a hitherto unreported excited singlet state that either converts to the triplet ground state or combines with a CO or solvent molecule to regenerate a penta-coordinated Fe species on a sub-picosecond timescale. This finding, which resolves the debate about the relative importance of different spin channels in the photochemistry of Fe(CO)5 (refs 4, 16,17,18,19 and 20), was made possible by the ability of femtosecond X-ray spectroscopy to probe frontier-orbital interactions with atom specificity. We expect the method to be broadly applicable in the chemical sciences, and to complement approaches that probe structural dynamics in ultrafast processes.
|
|
| 7. |
- Brena, Barbara, et al.
(författare)
-
InSb-TiOPc interfaces : Band alignment, ordering and structure dependent HOMO splitting
- 2009
-
Ingår i: Surface Science. - : Elsevier BV. - 0039-6028 .- 1879-2758. ; 603:20, s. 3160-3169
-
Tidskriftsartikel (refereegranskat)abstract
- Thin films of titanyl phthalocyanine (TiOPc) have been adsorbed on InSb(1 1 1) (3 x 3) and InSb(1 0 0) c(8 x 2) surfaces and studied with respect to their electronic structure using photoemission (PES), density functional theory (DFT) and scanning tunneling microscopy (STM). The interface chemical interaction is weak in both cases; no adsorbate induced surface band bending is observed and the energy level alignment across the interface is determined by the original position of the substrate Fermi level and the charge neutrality level of the molecule. Room temperature adsorption results in disordered films on both surfaces. The behaviors after annealing are different; on InSb(1 0 0) well-ordered molecular chains form along and on top of the In-rows, whereas on (1 1 1) no long range order is observed. The disorder leads to intermolecular interactions between the titanyl group and neighboring benzene rings leading to a split of TiOPc HOMO (highest occupied molecular orbital) by as much as 0.8 eV.
|
|
| 8. |
- Couto, Rafael C., et al.
(författare)
-
Anomalously strong two-electron one-photon X-ray decay transitions in CO caused by avoided crossing
- 2016
-
Ingår i: Scientific Reports. - : Nature Publishing Group. - 2045-2322. ; 6
-
Tidskriftsartikel (refereegranskat)abstract
- The unique opportunity to study and control electron-nuclear quantum dynamics in coupled potentials offered by the resonant inelastic X-ray scattering (RIXS) technique is utilized to unravel an anomalously strong two-electron one-photon transition from core-excited to Rydberg final states in the CO molecule. High-resolution RIXS measurements of CO in the energy region of 12-14 eV are presented and analyzed by means of quantum simulations using the wave packet propagation formalism and ab initio calculations of potential energy curves and transition dipole moments. The very good overall agreement between the experimental results and the theoretical predictions allows an in-depth interpretation of the salient spectral features in terms of Coulomb mixing of "dark" with "bright" final states leading to an effective two-electron one-photon transition. The present work illustrates that the improved spectral resolution of RIXS spectra achievable today may call for more advanced theories than what has been used in the past.
|
|
| 9. |
- Couto, Rafael C., et al.
(författare)
-
Coupled electron-nuclear dynamics in resonant 1 sigma -> 2 pi x-ray Raman scattering of CO molecules
- 2016
-
Ingår i: Physical Review A. - : American Physical Society. - 2469-9926. ; 93:3
-
Tidskriftsartikel (refereegranskat)abstract
- We present a detailed experimental-theoretical analysis of O K-edge resonant 1 sigma-2 pi inelastic x-ray scattering (RIXS) from carbon monoxide with unprecedented energy resolution. We employ high-level ab initio calculations to compute the potential energy curves of the states involved in the RIXS process and simulate the measured RIXS spectra using the wave-packet-propagation formalism, including Coulomb coupling in the final-state manifold. The theoretical analysis allows us to explain all the key features of the experimental spectra, including some that were not seen before. First, we clearly show the interference effect between different RIXS channels corresponding to the transition via orthogonal (1)Pi(x) and (1)Pi(y) core-excited states of CO. Second, the RIXS region of 13 eV energy loss presents a triple structure, revealed only by the high-resolution measurement. In previous studies, this region was attributed solely to a valence state. Here we show a strong Coulomb mixing of the Rydberg and valence final states, which opens the forbidden RIXS channels to the "dark" final Rydberg states and drastically changes the RIXS profile. Third, using a combination of high-resolution experiment and high-level theory, we improve the vertical bar 4 sigma(-1)2 pi(1)> final-state potential-energy curve by fitting its bottom part with the experiment. Also, the coupling constants between Rydberg and valence states were refined via comparison with the experiment. Our results illustrate the large potential of the RIXS technique for advanced studies of highly excited states of neutral molecules.
|
|
| 10. |
- Couto, Rafael C., et al.
(författare)
-
Coupled electron-nuclear dynamics in resonant 1σ→2π x-ray Raman scattering of CO molecules
- 2016
-
Ingår i: Physical Review A (Atomic, Molecular and Optical Physics). - 1050-2947. ; 93:3
-
Tidskriftsartikel (refereegranskat)abstract
- We present a detailed experimental-theoretical analysis of O K-edge resonant 1σ-2π inelastic x-ray scattering (RIXS) from carbon monoxide with unprecedented energy resolution. We employ high-level ab initio calculations to compute the potential energy curves of the states involved in the RIXS process and simulate the measured RIXS spectra using the wave-packet-propagation formalism, including Coulomb coupling in the final-state manifold. The theoretical analysis allows us to explain all the key features of the experimental spectra, including some that were not seen before. First, we clearly show the interference effect between different RIXS channels corresponding to the transition via orthogonal Πx1 and Πy1 core-excited states of CO. Second, the RIXS region of 13 eV energy loss presents a triple structure, revealed only by the high-resolution measurement. In previous studies, this region was attributed solely to a valence state. Here we show a strong Coulomb mixing of the Rydberg and valence final states, which opens the forbidden RIXS channels to the "dark" final Rydberg states and drastically changes the RIXS profile. Third, using a combination of high-resolution experiment and high-level theory, we improve the |4σ-12π1) final-state potential-energy curve by fitting its bottom part with the experiment. Also, the coupling constants between Rydberg and valence states were refined via comparison with the experiment. Our results illustrate the large potential of the RIXS technique for advanced studies of highly excited states of neutral molecules.
|
|
