Resonant inelastic X-ray spectroscopy of atoms and simple molecules: Satellite features and dependence on energy detuning and photon polarization

Žitnik, M.; Kavčič, M.; Bohinc, R.; Bučar, K.; Mihelič, A.; Cao, Wei; Guillemin, R.; Journel, L.; Marchenko, T.; Carniato, S.; Kawerk, Elie; Piancastelli, M. N.; Simon, M.

doi:10.1016/j.elspec.2015.05.018

Cited by 9 publications

(8 citation statements)

References 49 publications

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“…Previous studies have concluded that the initial dissociation dynamics of chlorinated molecules after the 1s ! ⇤ excitation are mostly determined by the coreexcited chlorine and the atom it is connected to (in our case this is always a carbon atom) 29,31,32,62 . The full set of vibrational normal modes were also decomposed and it was shown that the symmetric and antisymmetric C-Cl stretching are the major constituents of the initial movement upon 1s !…”

Section: Discussionmentioning

confidence: 99%

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Role of ultrafast dissociation in the fragmentation of chlorinated methanes

Kokkonen

Jänkälä

Patanen

et al. 2018

The Journal of Chemical Physics

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Photon-induced fragmentation of a full set of chlorinated methanes (CH3Cl, CH2Cl2, CHCl3, CCl4) has been investigated both experimentally and computationally. Using synchrotron radiation and electron-ion coincidence measurements, the dissociation processes were studied after chlorine 2p electron excitation. Experimental evidence for CH3Cl and CH2Cl2 contains unique features suggesting that fast dissociation processes take place. By contrast, CHCl3 and CCl4 molecules do not contain the same features, hinting that they experience alternative mechanisms for dissociation and charge migration. Computational work indicates differing rates of charge movement after the core-excitation, which can be used to explain the differences observed experimentally.

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Section: Discussionmentioning

confidence: 99%

“…Resonant inelastic X-ray scattering (RIXS) is also a common method for probing dissociation and nuclear dynamics. For chlorinated methanes RIXS has often been used in conjunction with carbon 1s excitation [28][29][30][31][32] .…”

Section: Introductionmentioning

confidence: 99%

Role of ultrafast dissociation in the fragmentation of chlorinated methanes

Kokkonen

Jänkälä

Patanen

et al. 2018

The Journal of Chemical Physics

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“…A special case here is the application of RIXS to the study of water and aqueous solutions and the chapter by Nilsson in this book includes this. Other noteworthy applications that reach over to molecular physics, address small molecules in the gas phase focusing on the dynamics in the core-excited intermediate states of RIXS (Marchenko et al, 2015, Zitnik et al, 2015. It has also been demonstrated that with high-enough spectral resolution, vibrational excitations can be probed with RIXS, (Vaz da Cruz et al, 2017), (Chapter by Nordgren Rubensson in this book).…”

Section: Introductionmentioning

confidence: 99%

Resonant Inelastic X-ray Scattering (RIXS) Studies in Chemistry: Present and Future

Lundberg¹,

Wernet²

2019

Synchrotron Light Sources and Free-Electron Lasers

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This chapter illustrates how resonant inelastic x-ray scattering (RIXS) is used to address questions in chemistry, with special focus on the electronic structure and catalytic activity of first row transition metals. RIXS is a two-photon process that is the x-ray equivalent of resonance Raman spectroscopy. The final states correspond to vibrational, valence electronic or even core excitations. In addition to the advantages of a local element-selective x-ray spectroscopic probe, RIXS gives new information compared to single-photon x-ray absorption and x-ray emission experiments. Metal L-edge RIXS shows intense metalcentered ligand-field transitions, even in cases where they are spin or parity forbidden in optical absorption spectroscopy. By selecting different resonances by appropriately tuning the incident energy, it is possible to isolate different ligand-field and charge-transfer transitions. The observation of a large number of electronic states that can be properly assigned, sometimes with the help of theoretical methods, gives novel opportunities to quantify metal-ligand interactions and their contributions to reactivity. RIXS in the K preedge can be used to obtain L-and M-edge like spectra including insight into charge-transfer excitations all with the advantages of a hard x-ray probe. Finally, it is shown how timeresolved RIXS down to the femtosecond timescale probes the orbitals of transient reaction intermediates. The usefulness of RIXS in chemistry is shown for a diverse set of systems, including coordination complexes, metal enzymes and nanoparticles.

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“…The photoinduced homolysis of the carbon–halogen bond in chlorinated hydrocarbons is a subject of intense research. − Recently, special attention has been paid to haloarenes ices. − The C–Cl bond photolysis of these compounds has been studied with vacuum ultraviolet (VUV) as well as X-ray radiation and aryl free radical coupling reactions have been observed. Exciting a core electron to an unoccupied orbital can lead to the homolysis of the carbon chlorine bond if the excited state has a strong dissociative potential. , On aryl halides, the transition probability to the first σ* state is high, and recent studies have shown that the C–Cl bond photolysis occurs after excitation to this state while the other bond distances of the molecule remain almost the same …”

Section: Introductionmentioning

confidence: 99%

Soft X-ray Chlorine Photolysis on Chlorobenzene Ice: An Experimental and Theoretical Study

et al. 2019

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An experimental and theoretical study of the photoinduced homolysis of the carbon-chlorine bond in an ice matrix of chlorobenzene is presented. A condensed chlorobenzene film has been grown in situ and near edge X-ray fine structure (NEXAFS) spectra were collected after exposing the condensed film to a monochromatic photon beam centered at the 2822 eV resonant excitation of chlorine and at 2850 eV. The photoabsorption to the Cl 1s → σ* and Cl 1s → π* states has been measured and the hypothesis of free radical coupling reactions was investigated via time-dependent density functional theory (TD-DFT) and complete active space self-consistent field (CASSCF) calculations. Also, potential energy pathways to the C–Cl cleavage have been obtained at the CASSCF level to the Cl 1s → σ*, 1s → π*, and 1s → ∞ states. A strong dissociative character was only found for the Cl 1s → σ* resonance.

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Resonant inelastic X-ray spectroscopy of atoms and simple molecules: Satellite features and dependence on energy detuning and photon polarization

Cited by 9 publications

References 49 publications

Role of ultrafast dissociation in the fragmentation of chlorinated methanes

Role of ultrafast dissociation in the fragmentation of chlorinated methanes

Resonant Inelastic X-ray Scattering (RIXS) Studies in Chemistry: Present and Future

Soft X-ray Chlorine Photolysis on Chlorobenzene Ice: An Experimental and Theoretical Study

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