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1. Ab Initio Simulations of Poorly- and Well-Equilibrated (CH3CN)n¯ Cluster Anions: Assigning Experimental Photoelectron Peaks to Surface-Bound Electrons and Solvated Monomer and Dimer Anions

   https://doi.org/10.1021/acs.jpca.1c05855  

   Narvaez, W. A. ; Schwartz, B. J. ( January 2021 , The journal of physical chemistry)

   Excess electrons in liquid acetonitrile are of particular interest because they exist in two different forms in equilibrium: they can be present as traditional solvated electrons in a cavity, and they can form some type of solvated molecular anion. Studies of small acetonitrile cluster anions in the gas phase show two isomers with distinct vertical detachment energies, and it is tempting to presume that the two gas-phase cluster anion isomers are precursors of the two excess electron species present in bulk solution. In this paper, we perform DFT-based ab initio molecular dynamics simulations of acetonitrile cluster anions to understand the electronic species that are present and why they have different binding energies. Using a long-range-corrected density functional that was optimally tuned to describe acetonitrile cluster anion structures, we have theoretically explored the chemistry of (CH3CN)n¯ cluster anions with sizes n=5,7 and 10. Since the temperature of the experimental cluster anions is not known, we performed two sets of simulations that investigated how the way in which the cluster anions are prepared affects the excess electron binding motif: one set of simulations simply attached excess electrons to neutral (CH3CN)n clusters, providing little opportunity for the clusters to relax in the presencemore »of the excess electron, while the other set allowed the cluster anions to thermally equilibrate near room temperature. We find that both sets of simulations show three distinct electron binding motifs: electrons can attach to the surface of the cluster (dipole-bound) or be present as either solvated monomer anions, CH3CN¯, or as solvated molecular dimer anions, (CH3CN)2¯. All three species have higher binding energies at larger cluster sizes. Thermal equilibration strongly favors the formation of the valence-bound molecular anions relative to surface-bound excess electrons, and the dimer anion becomes more stable than the monomer anion and surface-bound species as the cluster size increases. The calculated photoelectron spectra from our simulations in which there was poor thermal equilibration are in good agreement with experiment, suggesting assignment of the two experimental cluster anion isomers as the surface-bound electron and the solvated molecular dimer anion. The simulations also suggest that the shoulder seen experimentally on the low-energy isomer's detachment peak is not part of a vibronic progression but instead results from molecular monomer anions. Nowhere in the size range that we explore do we see evidence for a non-valence, cavity-bound interior-solvated electron, indicating that this species is likely only accessible at larger sizes with good thermal equilibration.« less
2. Extreme Ultraviolet Reflection-Absorption (XUV-RA) Spectroscopy: Probing Dynamics at Surfaces from a Molecular Perspective

   https://doi.org/https://doi.org/10.1021/acs.accounts.1c00765  

   Biswas, Somnath ; Baker, L. Robert ( March 2022 , Accounts of chemical research)

   Extreme ultraviolet (XUV) light sources based on high harmonic generation are enabling the development of novel spectroscopic methods to help advance the frontiers of ultrafast science and technology. In this account we discuss the development of XUV-RA spectroscopy at near grazing incident reflection geometry and highlight recent applications of this method to study ultrafast electron dynamics at surfaces. Measuring core-to-valence transitions with broadband, femtosecond pulses of XUV light extends the benefits of x-ray absorption spectroscopy to a laboratory tabletop by providing a chemical fingerprint of materials, including the ability to resolve individual elements with sensitivity to oxidation state, spin state, carrier polarity, and coordination geometry. Combining this chemical state sensitivity with femtosecond time resolution provides new insight into the material properties that govern charge carrier dynamics in complex materials. It is well known that surface dynamics differ significantly from equivalent processes in bulk materials, and that charge separation, trapping, transport, and recombination occurring uniquely at surfaces governs the efficiency of numerous technologically relevant processes spanning photocatalysis, photovoltaics, and information storage and processing. Importantly, XUV-RA spectroscopy at near grazing angle is also surface sensitive with a probe depth of 3 nm, providing a new window into electronic and structural dynamics atmore »surfaces and interfaces. Here we highlight the unique capabilities and recent applications of XUVRA spectroscopy to study photo-induced surface dynamics in metal oxide semiconductors, including photocatalytic oxides (Fe2O3, Co3O4 NiO, and CuFeO2) as well as photoswitchable magnetic oxide (CoFe2O4). We first compare the ultrafast electron self-trapping rates via small polaron formation at the surface and bulk of Fe2O3 where we note that the energetics and kinetics of this process differ significantly at the surface. Additionally, we demonstrate the ability to systematically tune this kinetics by molecular functionalization, thereby, providing a route to control carrier transport at surfaces. We also measure the spectral signatures of charge transfer excitons with site specific localization of both electrons and holes in a series of transition metal oxide semiconductors (Fe2O3, NiO, Co3O4). The presence of valence band holes probed at the oxygen L1-edge confirms a direct relationship between the metal-oxygen bond covalency and water oxidation efficiency. For a mixed metal oxide CuFeO2 in the layered delafossite structure, XUV-RA reveals that the sub-picosecond hole thermalization from O 2p to Cu 3d states of CuFeO2 leads to the spatial separation of electrons and holes, resulting in exceptional photocatalytic performance for H2 evolution and CO2 reduction of this material. Finally, we provide an example to show the ability of XUV-RA to probe spin state specific dynamics in a the photo-switchable ferrimagnet, cobalt ferrite (CoFe2O4). This study provides a detailed understating of ultrafast spin switching in a complex magnetic material with site-specific resolution. In summary, the applications of XUV-RA spectroscopy demonstrated here illustrate the current abilities and future promise of this method to extend molecule-level understanding from well-defined photochemical complexes to complex materials so that charge and spin dynamics at surfaces can be tuned with the precision of molecular photochemistry.« less
3. Excitation mechanisms in the intracluster filaments surrounding brightest cluster galaxies

   https://doi.org/10.1051/0004-6361/202039730  

   Polles, F. L. ; Salomé, P. ; Guillard, P. ; Godard, B. ; Pineau des Forêts, G. ; Olivares, V. ; Beckmann, R. S. ; Canning, R. E. ; Combes, F. ; Dubois, Y. ; et al ( July 2021 , Astronomy & Astrophysics)

   Context. The excitation of the filamentary gas structures surrounding giant elliptical galaxies at the center of cool-core clusters, also known as brightest cluster galaxies (BCGs), is key to our understanding of active galactic nucleus (AGN) feedback, and of the impact of environmental and local effects on star formation. Aims. We investigate the contribution of thermal radiation from the cooling flow surrounding BCGs to the excitation of the filaments. We explore the effects of small levels of extra heating (turbulence), and of metallicity, on the optical and infrared lines. Methods. Using the C LOUDY code, we modeled the photoionization and photodissociation of a slab of gas of optical depth A V  ≤ 30 mag at constant pressure in order to calculate self-consistently all of the gas phases, from ionized gas to molecular gas. The ionizing source is the extreme ultraviolet (EUV) and soft X-ray radiation emitted by the cooling gas. We tested these models comparing their predictions to the rich multi-wavelength observations from optical to submillimeter, now achieved in cool core clusters. Results. Such models of self-irradiated clouds, when reaching sufficiently large A V , lead to a cloud structure with ionized, atomic, and molecular gas phases. These models reproduce most ofmore »the multi-wavelength spectra observed in the nebulae surrounding the BCGs, not only the low-ionization nuclear emission region like optical diagnostics, [O  III ] λ 5007 Å/H β , [N  II ] λ 6583 Å/H α , and ([S  II ] λ 6716 Å+[S  II ] λ 6731 Å)/H α , but also the infrared emission lines from the atomic gas. [O  I ] λ 6300 Å/H α , instead, is overestimated across the full parameter space, except for very low A V . The modeled ro-vibrational H 2 lines also match observations, which indicates that near- and mid-infrared H 2 lines are mostly excited by collisions between H 2 molecules and secondary electrons produced naturally inside the cloud by the interaction between the X-rays and the cold gas in the filament. However, there is still some tension between ionized and molecular line tracers (i.e., CO), which requires optimization of the cloud structure and the density of the molecular zone. The limited range of parameters over which predictions match observations allows us to constrain, in spite of degeneracies in the parameter space, the intensity of X-ray radiation bathing filaments, as well as some of their physical properties like A V or the level of turbulent heating rate. Conclusions. The reprocessing of the EUV and X-ray radiation from the plasma cooling is an important powering source of line emission from filaments surrounding BCGs. C LOUDY self-irradiated X-ray excitation models coupled with a small level of turbulent heating manage to simultaneously reproduce a large number of optical-to-infrared line ratios when all the gas phases (from ionized to molecular) are modeled self-consistently. Releasing some of the simplifications of our model, like the constant pressure, or adding the radiation fields from the AGN and stars, as well as a combination of matter- and radiation-bounded cloud distribution, should improve the predictions of line emission from the different gas phases.« less
4. Enhanced Néel temperature in EuSnP under pressure

   https://doi.org/10.1039/c9dt00449a  

   Gui, Xin ; Finkelstein, Gregory J. ; Graf, David E. ; Wei, Kaya ; Zhang, Dongzhou ; Baumbach, Ryan E. ; Dera, Przemyslaw ; Xie, Weiwei ( April 2019 , Dalton Transactions)

   We present the combined results of single crystal X-ray diffraction, physical properties characterization, and theoretical assessment of EuSnP under high pressure. Single crystals of EuSnP prepared using Sn self-flux crystallize in the tetragonal NbCrN-type crystal structure (S.G. P 4/ nmm ) at ambient pressure. Previous studies have shown that for Eu ions, seven unpaired electrons impart a 2+ oxidation state. Assuming the oxidation states of Eu to be +2 and P to be −3, each Sn will donate one electron, with one p valence electron left for forming a weak Sn–Sn bond. According to the high-pressure single crystal X-ray diffraction measurements, no structural phase transition was observed up to ∼6.2 GPa. Temperature-dependent resistivity measurements up to 2.15 GPa on single crystals indicate that the phase-transition temperature occurring at the Néel temperature ( T N ) is significantly enhanced under high pressure. The robust crystallography and enhanced antiferromagnetic transition temperatures can be rationalized by the electronic structure calculations and chemical bonding analysis. The increasing Eu–P bonding interaction is consistent with the lattice parameter changing and enhanced T N . Moreover, the molecular orbital diagram shows that the weak Sn–Sn bond can be squeezed under pressure, acting as a compression buffer tomore »stabilize the structure.« less
5. Nonadiabatic coupling of the dynamical structure to the superconductivity in YSr ₂ Cu _2.75 Mo _0.25 O _7.54 and Sr ₂ CuO _3.3

   https://doi.org/10.1073/pnas.2018336117  

   Conradson, Steven D. ; Geballe, Theodore H. ; Jin, Chang-Qing ; Cao, Li-Peng ; Gauzzi, Andrea ; Karppinen, Maarit ; Baldinozzi, Gianguido ; Li, Wen-Min ; Gilioli, Edmondo ; Jiang, Jack M. ; et al ( December 2020 , Proceedings of the National Academy of Sciences)

   A crucial issue in cuprates is the extent and mechanism of the coupling of the lattice to the electrons and the superconductivity. Here we report Cu K edge extended X-ray absorption fine structure measurements elucidating the internal quantum tunneling polaron (iqtp) component of the dynamical structure in two heavily overdoped superconducting cuprate compounds, tetragonal YSr 2 Cu 2.75 Mo 0.25 O 7.54 with superconducting critical temperature, T c = 84 K and hole density p = 0.3 to 0.5 per planar Cu, and the tetragonal phase of Sr 2 CuO 3.3 with T c = 95 K and p = 0.6. In YSr 2 Cu 2.75 Mo 0.25 O 7.54 changes in the Cu-apical O two-site distribution reflect a sequential renormalization of the double-well potential of this site beginning at T c , with the energy difference between the two minima increasing by ∼6 meV between T c and 52 K. Sr 2 CuO 3.3 undergoes a radically larger transformation at T c , >1-Å displacements of the apical O atoms. The principal feature of the dynamical structure underlying these transformations is the strongly anharmonic oscillation of the apical O atoms in a double-well potential that results in the observationmore »of two distinct O sites whose Cu–O distances indicate different bonding modes and valence-charge distributions. The coupling of the superconductivity to the iqtp that originates in this nonadiabatic coupling between the electrons and lattice demonstrates an important role for the dynamical structure whereby pairing occurs even in a system where displacements of the atoms that are part of the transition are sufficiently large to alter the Fermi surface. The synchronization and dynamic coherence of the iqtps resulting from the strong interactions within a crystal would be expected to influence this process.« less