| 1. |
- Banerjee, Ambar, 1985-, et al.
(författare)
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Accessing metal-specific orbital interactions in C–H activation with resonant inelastic X-ray scattering
- 2024
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Ingår i: Chemical Science. - : Royal Society of Chemistry. - 2041-6520 .- 2041-6539. ; 15:7, s. 2398-2409
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Tidskriftsartikel (refereegranskat)abstract
- Photochemically prepared transition-metal complexes are known to be effective at cleaving the strong C–H bonds of organic molecules in room temperature solutions. There is also ample theoretical evidence that the two-way, metal to ligand (MLCT) and ligand to metal (LMCT), charge-transfer between an incoming alkane C–H group and the transition metal is the decisive interaction in the C–H activation reaction. What is missing, however, are experimental methods to directly probe these interactions in order to reveal what determines reactivity of intermediates and the rate of the reaction. Here, using quantum chemical simulations we predict and propose future time-resolved valence-to-core resonant inelastic X-ray scattering (VtC-RIXS) experiments at the transition metal L-edge as a method to provide a full account of the evolution of metal–alkane interactions during transition-metal mediated C–H activation reactions. For the model system cyclopentadienyl rhodium dicarbonyl (CpRh(CO)2), we demonstrate, by simulating the VtC-RIXS signatures of key intermediates in the C–H activation pathway, how the Rh-centered valence-excited states accessible through VtC-RIXS directly reflect changes in donation and back-donation between the alkane C–H group and the transition metal as the reaction proceeds via those intermediates. We benchmark and validate our quantum chemical simulations against experimental steady-state measurements of CpRh(CO)2 and Rh(acac)(CO)2 (where acac is acetylacetonate). Our study constitutes the first step towards establishing VtC-RIXS as a new experimental observable for probing reactivity of C–H activation reactions. More generally, the study further motivates the use of time-resolved VtC-RIXS to follow the valence electronic structure evolution along photochemical, photoinitiated and photocatalytic reactions with transition metal complexes.
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| 2. |
- Berholts, Marta, et al.
(författare)
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Quantum watch and its intrinsic proof of accuracy
- 2022
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Ingår i: Physical Review Research. - : American Physical Society. - 2643-1564. ; 4:4
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Tidskriftsartikel (refereegranskat)abstract
- We have investigated the rich dynamics of complex wave packets composed of multiple high-lying Rydbergstates in He. A quantitative agreement is found between theory and time-resolved photoelectron spectroscopyexperiments. We show that the intricate time dependence of such wave packets can be used for investigatingquantum defects and performing artifact-free timekeeping. The latter relies on the unique fingerprint that iscreated by the time-dependent photoionization of these complex wave packets. These fingerprints determinehow much time has passed since the wave packet was formed and provide an assurance that the measured time iscorrect. Unlike any other clock, this quantum watch does not utilize a counter and is fully quantum mechanicalin its nature. The quantum watch has the potential to become an invaluable tool in pump-probe spectroscopy dueto its simplicity, assurance of accuracy, and ability to provide an absolute timestamp, i.e., there is no need to findtime zero.
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| 3. |
- Gupta, Rahul, et al.
(författare)
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Element-resolved evidence of superdiffusive spin current arising from ultrafast demagnetization process
- 2023
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Ingår i: Phys. Rev. B. - : American Physical Society. ; 108:6
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Tidskriftsartikel (refereegranskat)abstract
- Using element-specific measurements of the ultrafast demagnetization of Ru/Fe65Co35 hetero-structures, we show that Ru can exhibit a significant magnetic contrast (3% asymmetry) resulting from ultrafast spin currents emanating from the demagnetization process of the FeCo layer. We use this magnetic contrast to investigate how superdiffusive spin currents are affected by the doping of heavy elements in the FeCo layer. We find that the spin currents are strongly suppressed, and that the recovery process in Ru slows down by Re doping. This is in accordance with a change in interface reflectivity of spin currents as found by the superdiffusive spin transport model.
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| 4. |
- Jana, Somnath, et al.
(författare)
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A setup for element specific magnetization dynamics using the transverse magneto-optic Kerr effect in the energy range of 30-72 eV
- 2017
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Ingår i: Review of Scientific Instruments. - : AMER INST PHYSICS. - 0034-6748 .- 1089-7623. ; 88:3
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Tidskriftsartikel (refereegranskat)abstract
- In this paper, we present a spectrometer that is designed for element-specific and time-resolved transverse magneto-optic Kerr effect experiments at the high-harmonic generation pump-probe facility High Energy Laser Induced Overtone Source (HELIOS) laboratory. HELIOS delivers photons with energies between 30 eV and 72 eV with an overall time resolution of less than 40 fs. The spectrometer is based on a Rowland-circle geometry and allows for simultaneous measurements of all magnetic transition-metal elements. The setup also features easy sample transfer and alignment, and it combines high photon throughput, optimized data acquisition, and a fast switching of the magnetic field at the sample. The spectrometer performance is demonstrated by measuring the ultrafast demagnetization of permalloy. Our data are, for all practical purposes, identical to what have been reported in the earlier high-order harmonic generation work of a similar sample by Mathias et al. [Proc. Natl. Acad. Sci. U.S.A. 109, 4792-4797 (2012)], however, obtained within 15% of the acquisition time compared to their study. Furthermore, our data show a shift of the demagnetization curve of Ni relative to Fe, which has previously been interpreted as a delay of the Ni demagnetization to that of Fe [S. Mathias et al., Proc. Natl. Acad. Sci. U. S. A. 109, 4792-4797 (2012)].
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| 5. |
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| 6. |
- Jana, Somnath, et al.
(författare)
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Analysis of the linear relationship between asymmetry and magnetic moment at the M edge of 3d transition metals
- 2020
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Ingår i: Physical Review Research. - : American Physical Society. - 2643-1564. ; 2:1
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Tidskriftsartikel (refereegranskat)abstract
- The magneto-optical response of Fe and Ni during ultrafast demagnetization is studied experimentally and theoretically. We have performed pump-probe experiments in the transverse magneto-optical Kerr effect (T-MOKE) geometry using photon energies that cover the M absorption edges of Fe and Ni between 40 and 72 eV. The magnetic asymmetry was obtained by forming the difference of reflected intensities obtained for two opposite orientations of the sample magnetization. Density functional theory (DFT) was used to calculate the magneto-optical response of different magnetic configurations, representing different types of excitations: long wavelength magnons, short wavelength magnons, and Stoner excitations. In the case of Fe, we find that the calculated asymmetry is strongly dependent on the specific type of magnetic excitation. Our modeling also reveals that during remagnetization Fe is, to a reasonable approximation, described by magnons, even though small nonlinear contributions could indicate some degree of Stoner excitations as well. In contrast, we find that the calculated asymmetry in Ni is rather insensitive to the type of magnetic excitations. However, there is a weak nonlinearity in the relation between asymmetry and the off-diagonal component of the dielectric tensor, which does not originate from the modifications of the electronic structure. Our experimental and theoretical results thus emphasize the need to consider a coupling between asymmetry and magnetization that may be more complex than a simple linear relationship. This insight is crucial for the microscopic interpretation of ultrafast magnetization experiments.
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| 7. |
- Jana, Somnath, et al.
(författare)
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Atom-specific magnon driven ultrafast spin dynamics in Fe1-xNix alloys
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Annan publikation (övrigt vetenskapligt/konstnärligt)abstract
- By employing element specific ultrafast spectroscopy in Fe1-xNix alloys alloys, we find a composition dependent effect in the demagnetization that we relate to changes in electron-magnon scattering. In all six measured alloys of different composition, the demagnetization of Ni compared to Fe exhibits a delay, an effect which we find is inherent in alloys but not in elemental Fe and Ni. Using a model based on electron-magnon scattering, we extract a spin-wave stiffness from all alloys that show excellent agreement with values obtained from other techniques. The result establishes the atom-specific sd-exchange induced magnon generation as an underlying mechanism during ultrafast demagnetization in Fe1-xNix alloys
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| 8. |
- Jana, Somnath, et al.
(författare)
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Atom-specific magnon-driven ultrafast spin dynamics in Fe1-xNix alloys
- 2023
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Ingår i: Physical Review B. - : American Physical Society (APS). - 2469-9950 .- 2469-9969. ; 107:18
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Tidskriftsartikel (refereegranskat)abstract
- By employing element-specific spectroscopy in the ultrafast time scale in Fe1-xNix alloys, we find a composition-dependent effect in the demagnetization that we relate to electron-magnon scattering and changes in the spin-wave stiffness. In all six measured alloys of different composition, the demagnetization of Ni compared to Fe exhibits a delay, an effect which we find is inherent in alloys but not in elemental Fe and Ni. Using a model based on electron-magnon scattering, we extract a spin-wave stiffness from all alloys that show excellent agreement with values obtained from other techniques.
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| 9. |
- Jana, S., et al.
(författare)
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Experimental confirmation of the delayed Ni demagnetization in FeNi alloy
- 2022
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Ingår i: Applied Physics Letters. - : AIP Publishing. - 0003-6951 .- 1077-3118. ; 120
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Tidskriftsartikel (refereegranskat)abstract
- Element-selective techniques are central for the understanding of ultrafast spin dynamics in multi-element materials, such as magnetic alloys. Recently, however, it turned out that the commonly used technique of the transverse magneto-optical Kerr effect (T-MOKE) in the extreme ultraviolet range may have issues with unwanted crosstalk between different elemental signals and energy-dependent non-linear response. This problem can be sizeable, which puts recent observations of ultrafast spin transfer from Fe to Ni sites in FeNi alloys into question. In this study, we investigate the Fe-to-Ni spin transfer in a crosstalk-free time-resolved x-ray magnetic circular dichroism (XMCD) experiment with a reliable time reference. With XMCD near the absorption maxima, we find a very similar Fe and Ni dynamics as with T-MOKE from identical samples. Considering the potential non-linearities of the T-MOKE response, such a good agreement in our findings is remarkable. Our data provide the ongoing discussion about ultrafast spin-transfer mechanisms in FeNi systems with a broader experimental basis.
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| 10. |
- Jay, Raphael, et al.
(författare)
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Tracking C–H activation with orbital resolution
- 2023
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Ingår i: Science. - : American Association for the Advancement of Science (AAAS). - 0036-8075 .- 1095-9203. ; 380:6648, s. 955-960
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Tidskriftsartikel (refereegranskat)abstract
- Transition metal reactivity toward carbon-hydrogen (C-H) bonds hinges on the interplay of electron donation and withdrawal at the metal center. Manipulating this reactivity in a controlled way is difficult because the hypothesized metal-alkane charge-transfer interactions are challenging to access experimentally. Using time-resolved x-ray spectroscopy, we track the charge-transfer interactions during C-H activation of octane by a cyclopentadienyl rhodium carbonyl complex. Changes in oxidation state as well as valence-orbital energies and character emerge in the data on a femtosecond to nanosecond timescale. The x-ray spectroscopic signatures reflect how alkane-to-metal donation determines metal-alkane complex stability and how metal-to-alkane back-donation facilitates C-H bond cleavage by oxidative addition. The ability to dissect charge-transfer interactions on an orbital level provides opportunities for manipulating C-H reactivity at transition metals.
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