Mapping chemical bonding of reaction intermediates with femtosecond X-ray laser spectroscopy

Wernet, Philippe; Beye, Martin; Groot, Frank M. F. de; Düsterer, S.; Gaffney, Kelly J.; Grübel, S.; Hartsock, Robert J.; Hennies, Franz; Josefsson, Ida; Kennedy, Brian; Kunnus, Kristjan; Leitner, Torsten; Mazza, Tommaso; Meyer, Michael; Nordlund, Dennis; Odelius, Michael; Quevedo, Wilson; Radcliffe, P.; Rajković, Ivan; Schlotter, B.; Scholz, Mirko; Schreck, Simon; Suljoti, Edlira; Techert, Simone; Turner, James J.; Weniger, Christian; Zhang, W.; Föhlisch, Alexander

doi:10.1051/epjconf/20134105025

Cited by 4 publications

(3 citation statements)

References 6 publications

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“…The ultrafast dynamics of CO release in metal carbonyls has been investigated for many compounds and under various conditions. Probably the substance studied in most detail is iron pentacarbonyl Fe(CO) 5 , whose photodissociation has been studied in the gas phase via transient ionization with different laser wavelengths − or by transient electron diffraction and in solution with infrared − or X-ray , transient absorption. These studies corroborate the great interest in the initial steps of CO photolysis from metal carbonyls and underline the multifaceted reaction pathways that may occur.…”

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confidence: 99%

Ultrafast Photochemistry of a Manganese-Tricarbonyl CO-Releasing Molecule (CORM) in Aqueous Solution

Rudolf

Kanal

Knorr

et al. 2013

J. Phys. Chem. Lett.

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Ultraviolet irradiation of a manganese-tricarbonyl CO-releasing molecule (CORM) in water eventually leads to the liberation of some of the carbon monoxide ligands. By ultraviolet pump/mid-infrared probe femtosecond transient absorption spectroscopy in combination with quantum chemical calculations, we could disclose for the exemplary compound [Mn(CO)3(tpm)](+) (tpm = tris(2-pyrazolyl)methane) that only one of the three carbonyl ligands is photochemically dissociated on an ultrafast time scale and that some molecules may undergo geminate recombination.

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confidence: 99%

Ultrafast Photochemistry of a Manganese-Tricarbonyl CO-Releasing Molecule (CORM) in Aqueous Solution

Rudolf

Kanal

Knorr

et al. 2013

J. Phys. Chem. Lett.

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“…Inelastic scattering approach has progressed a stage further at the soft X-ray laser FLASH (Hamburg), which allowed a study of the photochemistry of Fe(CO) 5 using the Fe L III absorption edge. 46 The emission spectrometer was used to record RIXS spectra at very high time resolution, such that a feature could be distinguished from those due to the solvated Fe(CO) 5 itself and assigned to Fe(CO) 4 . Using that, the build up of the coordinatively unsaturated intermediate could indeed be monitored.…”

Section: Ultrafast X-ray Techniques and Dynamicsmentioning

confidence: 99%

Dynamic structure elucidation of chemical reactivity by laser pulses and X-ray probes

2015

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Visualising chemical reactions by X-ray methods is a tantalising prospect. New light sources provide the prospect for studying atomic, electronic and energy transfers accompanying chemical change by X-ray spectroscopy and inelastic scattering. Here we assess how this adventure can illuminate inorganic and catalytic chemistry. In particular X-ray inelastic scattering provides a means of exploiting X-ray free electron lasers, as a parallel to laser Raman spectroscopy.

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“…At the molecular scale, electron transfer and electron redistribution processes are considered as important dynamical signatures for molecular electronics. With conjugate electronic systems, several molecules have been shown as suitable candidates for this type of applications. − Recently, great attention has been given to the role of molecular orbitals in the static structure of molecules , and in the dynamical process during interaction with light. − Among these molecules stilbene and azobenzene (AZB), provide benchmark for the fundamental studies of electron transfer in complex systems, where they are switchable via push–pull isomerization. This isomerization, intensively studied in the UV–vis regime, − can usually be achieved, when light falls on the molecule in the electronic ground state.…”

Section: Introductionmentioning

confidence: 99%

Tracking of Azobenzene Isomerization by X-ray Emission Spectroscopy

Ebadi

2014

J. Phys. Chem. A

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Cis-trans isomerizations are among the fundamental processes in photochemistry. In azobenzene or its derivatives this dynamics is, due to its reversibility, one of the reactions widely used in photostimulation of molecular motors or in molecular electronics. Though intensively investigated in the optical regime, no detailed study exists in the X-ray regime so far. Because the X-ray emission spectroscopy echoes the electronic structure sensitive to the geometry, this theoretical report based on the density functional theory and its time-dependent version presents different nitrogen K-edge X-ray emission spectra for cis and trans isomers with close interrelation to their electron configuration. Considering the spectrum along the isomerization path, these structural signatures can be utilized to probe the isomerization dynamics in the excited molecule. The scheme can further be generalized to the element specific photoreactions.

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Mapping chemical bonding of reaction intermediates with femtosecond X-ray laser spectroscopy

Abstract: Abstract. We determine the pathways in the photo-dissociation reactions of Fe(CO) 5 both in the gas phase and in solution by mapping the valence electronic structure of the reaction intermediates with femtosecond X-ray laser spectroscopy.

Cited by 4 publications

References 6 publications

Ultrafast Photochemistry of a Manganese-Tricarbonyl CO-Releasing Molecule (CORM) in Aqueous Solution

Ultrafast Photochemistry of a Manganese-Tricarbonyl CO-Releasing Molecule (CORM) in Aqueous Solution

Dynamic structure elucidation of chemical reactivity by laser pulses and X-ray probes

Tracking of Azobenzene Isomerization by X-ray Emission Spectroscopy

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