Photocatalysis that uses the energy of light to promote chemical transformations by exploiting the reactivity of excited-state molecules is at the heart of a virtuous dynamic within the chemical community. Visible-light metal-based photosensitizers are most prominent in organic synthesis, thanks to their versatile ligand structure tunability allowing to adjust photocatalytic properties toward specific applications. Nevertheless, a large majority of these photocatalysts are cationic species whose counterion effects remain underestimated and overlooked. In this report, we show that modification of the X counterions constitutive of [Ru(bpy)3](X)2 photocatalysts modulates their catalytic activities in intermolecular [2 + 2] cycloaddition reactions operating through triplet–triplet energy transfer (TTEnT). Particularly noteworthy is the dramatic impact observed in low-dielectric constant solvent over the excited-state quenching coefficient, which varies by two orders of magnitude depending on whether X is a large weakly bound (BArF4–) or a tightly bound (TsO–) anion. In addition, the counterion identity also greatly affects the photophysical properties of the cationic ruthenium complex, with [Ru(bpy)3](BArF4)2 exhibiting the shortest 3MLCT excited-state lifetime, highest excited state energy, and highest photostability, enabling remarkably enhanced performance (up to >1000 TON at a low 500 ppm catalyst loading) in TTEnT photocatalysis. These findings supported by density functional theory-based calculations demonstrate that counterions have a critical role in modulating cationic transition metal-based photocatalyst potency, a parameter that should be taken into consideration also when developing energy transfer-triggered processes.

Continuer la lecture Share

Actinide +IV complexes with six nitrates [AnIV(NO3)6]2− (An = Th, U, Np, and Pu) have been studied by 15N and 17O NMR spectroscopy in solution and first-principles calculations. Magnetic susceptibilities were evaluated experimentally using the Evans method and are in good agreement with the ab initio values. The evolution in the series of the crystal field parameters deduced from ab initio calculations is discussed. The NMR paramagnetic shifts are analyzed based on ab initio calculations. Because the cubic symmetry of the complex quenches the dipolar contribution, they are only of Fermi contact origin. They are evaluated from first-principles based on a complete active space/density functional theory (DFT) strategy, in good accordance with the experimental one. The ligand hyperfine coupling constants are deduced from paramagnetic shifts and calculated using unrestricted DFT. The latter are decomposed in terms of the contribution of molecular orbitals. It highlights two pathways for the delocalization of the spin density from the metallic open-shell 5f orbitals to the NMR active nuclei, either through the valence 5f hybridized with 6d to the valence 2p molecular orbitals of the ligands, or by spin polarization of the metallic 6p orbitals which interact with the 2s-based molecular orbitals of the ligands.

Continuer la lecture Share

Mid-infrared emission features probe the properties of ionized gas, and hot or warm molecular gas. The Orion Bar is a frequently studied photodissociation region (PDR) containing large amounts of gas under these conditions, and was observed with the MIRI IFU aboard JWST as part of the "PDRs4All" program. The resulting IR spectroscopic images of high angular resolution (0.2") reveal a rich observational inventory of mid-IR emission lines, and spatially resolve the substructure of the PDR, with a mosaic cutting perpendicularly across the ionization front and three dissociation fronts. We extracted five spectra that represent the ionized, atomic, and molecular gas layers, and measured the most prominent gas emission lines. An initial analysis summarizes the physical conditions of the gas and the potential of these data. We identified around 100 lines, report an additional 18 lines that remain unidentified, and measured the line intensities and central wavelengths. The H I recombination lines originating from the ionized gas layer bordering the PDR, have intensity ratios that are well matched by emissivity coefficients from H recombination theory, but deviate up to 10% due contamination by He I lines. We report the observed emission lines of various ionization stages of Ne, P, S, Cl, Ar, Fe, and Ni, and show how certain line ratios vary between the five regions. We observe the pure-rotational H$_2$ lines in the vibrational ground state from 0-0 S(1) to 0-0 S(8), and in the first vibrationally excited state from 1-1 S(5) to 1-1 S(9). We derive H$_2$ excitation diagrams, and approximate the excitation with one thermal (~700 K) component representative of an average gas temperature, and one non-thermal component (~2700 K) probing the effect of UV pumping. We compare these results to an existing model for the Orion Bar PDR and highlight the differences with the observations.

Continuer la lecture Share

We study the random transverse field Ising model on a finite Cayley tree. This enables us to probe key questions arising in other important disordered quantum systems, in particular the Anderson transition and the problem of dirty bosons on the Cayley tree, or the emergence of non-ergodic properties in such systems. We numerically investigate this problem building on the cavity mean-field method complemented by state-of-the art finite-size scaling analysis. Our numerics agree very well with analytical results based on an analogy with the traveling wave problem of a branching random walk in the presence of an absorbing wall. Critical properties and finite-size corrections for the zero-temperature paramagnetic-ferromagnetic transition are studied both for constant and algebraically vanishing boundary conditions. In the later case, we reveal a regime which is reminiscent of the non-ergodic delocalized phase observed in other systems, thus shedding some light on critical issues in the context of disordered quantum systems, such as Anderson transitions, the many-body localization or disordered bosons in infinite dimensions.

Continuer la lecture Share