Nonadiabatic Charge Transfer within Photoexcited Nickel Porphyrins.

Metalloporphyrins with open d-shell ions can drive biochemical energy cycles. However, their utilization in photoconversion is hampered by rapid deactivation. Mapping the relaxation pathways is essential for elaborating strategies that can favorably alter the charge dynamics through chemical design and photoexcitation conditions. Here, we combine transient optical absorption spectroscopy and transient X-ray emission spectroscopy with femtosecond resolution to probe directly the coupled electronic and spin dynamics within a photoexcited nickel porphyrin in solution. Measurements and calculations reveal that a state with charge-transfer character mediates the formation of the thermalized excited state, thereby advancing the description of the photocycle for this important representative molecule. More generally, establishing that intramolecular charge-transfer steps play a role in the photoinduced dynamics of metalloporphyrins with open d-shell sets a conceptual ground for their development as building blocks capable of boosting nonadiabatic photoconversion in functional architectures through "hot" charge transfer down to the attosecond time scale.

[Tobacco and tuberculosis: the nature of the links and the consequences of this association]. / Tabac et tuberculose : nature des liens et conséquences de cette association.

Tuberculosis and smoking are responsible for significant mortality worldwide. Smoking is spreading in emerging countries, and its prevalence is high in developed countries among socially disadvantaged populations; it could be the source of a resurgence of tuberculosis in future years. The aim of this review is to clarify the consequences of the association between smoking and tuberculosis, and the benefits of smoking cessation for smokers with tuberculosis.

Ultrafast Jahn-Teller Photoswitching in Cobalt Single-Ion Magnets.

Single-ion magnets (SIMs) constitute the ultimate size limit in the quest for miniaturizing magnetic materials. Several bottlenecks currently hindering breakthroughs in quantum information and communication technologies could be alleviated by new generations of SIMs displaying multifunctionality. Here, ultrafast optical absorption spectroscopy and X-ray emission spectroscopy are employed to track the photoinduced spin-state switching of the prototypical complex [Co(terpy)2 ]2+ (terpy = 2,2':6',2″-terpyridine) in solution phase. The combined measurements and their analysis supported by density functional theory (DFT), time-dependent-DFT (TD-DFT) and multireference quantum chemistry calculations reveal that the complex undergoes a spin-state transition from a tetragonally elongated doublet state to a tetragonally compressed quartet state on the femtosecond timescale, i.e., it sustains ultrafast Jahn-Teller (JT) photoswitching between two different spin multiplicities. Adding new Co-based complexes as possible contenders in the search for JT photoswitching SIMs will greatly widen the possibilities for implementing magnetic multifunctionality and eventually controlling ultrafast magnetization with optical photons.

Optimizing the quasi-equilibrium state of hot carriers in all-inorganic lead halide perovskite nanocrystals through Mn doping: fundamental dynamics and device perspectives.

Hot carrier (HC) cooling accounts for the significant energy loss in lead halide perovskite (LHP) solar cells. Here, we study HC relaxation dynamics in Mn-doped LHP CsPbI3 nanocrystals (NCs), combining transient absorption spectroscopy and density functional theory (DFT) calculations. We demonstrate that Mn2+ doping (1) enlarges the longitudinal optical (LO)-acoustic phonon bandgap, (2) enhances the electron-LO phonon coupling strength, and (3) adds HC relaxation pathways via Mn orbitals within the bands. The spectroscopic study shows that the HC cooling process is decelerated after doping under band-edge excitation due to the dominant phonon bandgap enlargement. When the excitation photon energy is larger than the optical bandgap and the Mn2+ transition gap, the doping accelerates the cooling rate owing to the dominant effect of enhanced carrier-phonon coupling and relaxation pathways. We demonstrate that such a phenomenon is optimal for the application of hot carrier solar cells. The enhanced electron-LO phonon coupling and accelerated cooling of high-temperature hot carriers efficiently establish a high-temperature thermal quasi-equilibrium where the excessive energy of the hot carriers is transferred to heat the cold carriers. On the other hand, the enlarged phononic band-gap prevents further cooling of such a quasi-equilibrium, which facilitates the energy conversion process. Our results manifest a straightforward methodology to optimize the HC dynamics for hot carrier solar cells by element doping.

Visualizing Light-Induced Microstrain and Phase Transition in Lead-Free Perovskites Using Time-Resolved X-Ray Diffraction.

Metal halide perovskites have emerged as promising materials for optoelectronic applications in the last decade. A large amount of effort has been made to investigate the interplay between the crystalline lattice and photoexcited charge carriers as it is vital to their optoelectronic performance. Among them, ultrafast laser spectroscopy has been intensively utilized to explore the charge carrier dynamics of perovskites, from which the local structural information can only be extracted indirectly. Here, we have applied a time-resolved X-ray diffraction technique to investigate the structural dynamics of prototypical two-dimensional lead-free halide perovskite Cs3Bi2Br9 nanoparticles across temporal scales from 80 ps to microseconds. We observed a quick recoverable (a few ns) photoinduced microstrain up to 0.15% and a long existing lattice expansion (∼a few hundred nanoseconds) at mild laser fluence. Once the laser flux exceeds 1.4 mJ/cm2, the microstrain saturates and the crystalline phase partially transfers into a disordered phase. This photoinduced transient structural change can recover within the nanosecond time scale. These results indicate that photoexcitation of charge carriers couples with lattice distortion, which fundamentally affects the dielectric environment and charge carrier transport.

Ultrafast charge transfer dynamics in 2D covalent organic frameworks/Re-complex hybrid photocatalyst.

Rhenium(I)-carbonyl-diimine complexes have emerged as promising photocatalysts for carbon dioxide reduction with covalent organic frameworks recognized as perfect sensitizers and scaffold support. Such Re complexes/covalent organic frameworks hybrid catalysts have demonstrated high carbon dioxide reduction activities but with strong excitation energy-dependence. In this paper, we rationalize this behavior by the excitation energy-dependent pathways of internal photo-induced charge transfer studied via transient optical spectroscopies and time-dependent density-functional theory calculation. Under band-edge excitation, the excited electrons are quickly injected from covalent organic frameworks moiety into catalytic RheniumI center within picosecond but followed by fast backward geminate recombination. While under excitation with high-energy photon, the injected electrons are located at high-energy levels in RheniumI centers with longer lifetime. Besides those injected electrons to RheniumI center, there still remain some long-lived electrons in covalent organic frameworks moiety which is transferred back from RheniumI. This facilitates the two-electron reaction of carbon dioxide conversion to carbon monoxide.

Free Carriers versus Self-Trapped Excitons at Different Facets of Ruddlesden-Popper Two-Dimensional Lead Halide Perovskite Single Crystals.

The physical origin of sub-band gap photoluminescence in Ruddlesden-Poppers two-dimensional (2D) lead halide perovskites (LHPs) is still under debate. In this paper, we studied the photoluminescence features from two different facets of 2D LHP single crystals: the in-plane facet (IF) containing the 2D inorganic layers and the facet perpendicular to the 2D layers (PF). At the IF, the free carriers (FCs) dominate due to the weak electron-phonon coupling in a symmetric lattice. At the PF, the strain accumulation along the 2D layers enhances the electron-phonon coupling and facilitates self-trapped exciton (STE) formation. The time-resolved PL studies indicate that free carriers (FCs) at the IF can move freely and display the trapping by the intrinsic defects. The STEs at the PF are not likely trapped by the defects due to the reduced mobility. However, with increasing STE density, the STE transport is promoted, enabling the trapping of STE by the intrinsic defects.

Structural Study of the Photo-Mediated Growth of Silver Nanoprisms.

We present a small-angle X-ray scattering (SAXS) study of the anisotropic photoinduced growth of silver (Ag) nanoprisms in aqueous dispersions. The growth of nearly spherical (<10 nm) Ag particles into large (>40 nm) and thin (<10 nm) triangular nanoprisms induced by 550 nm laser is followed in terms of particle size using indirect and direct methods for irradiation times up to 150 min. During the process, the surface-to-volume ratio of the particles decreased. The SAXS data of the initial solution fit well to the model of polydisperse spheres with pronounced average diameters around 7.4 nm and 10 nm. The data after 45 min irradiation fit well to the model containing approximately the same amount of the initial particles and the end product, the nanoprisms.

Ultrafast hot-hole injection modifies hot-electron dynamics in Au/p-GaN heterostructures.

A fundamental understanding of hot-carrier dynamics in photo-excited metal nanostructures is needed to unlock their potential for photodetection and photocatalysis. Despite numerous studies on the ultrafast dynamics of hot electrons, so far, the temporal evolution of hot holes in metal-semiconductor heterostructures remains unknown. Here, we report ultrafast (t < 200 fs) hot-hole injection from Au nanoparticles into the valence band of p-type GaN. The removal of hot holes from below the Au Fermi level is observed to substantially alter the thermalization dynamics of hot electrons, reducing the peak electronic temperature and the electron-phonon coupling time of the Au nanoparticles. First-principles calculations reveal that hot-hole injection modifies the relaxation dynamics of hot electrons in Au nanoparticles by modulating the electronic structure of the metal on timescales commensurate with electron-electron scattering. These results advance our understanding of hot-hole dynamics in metal-semiconductor heterostructures and offer additional strategies for manipulating the dynamics of hot carriers on ultrafast timescales.

Exploring the light-induced dynamics in solvated metallogrid complexes with femtosecond pulses across the electromagnetic spectrum.

Oligonuclear complexes of d4-d7 transition metal ion centers that undergo spin-switching have long been developed for their practical role in molecular electronics. Recently, they also have appeared as promising photochemical reactants demonstrating improved stability. However, the lack of knowledge about their photophysical properties in the solution phase compared to mononuclear complexes is currently hampering their inclusion into advanced light-driven reactions. In the present study, the ultrafast photoinduced dynamics in a solvated [2 × 2] iron(II) metallogrid complex are characterized by combining measurements with transient optical-infrared absorption and x-ray emission spectroscopy on the femtosecond time scale. The analysis is supported by density functional theory calculations. The photocycle can be described in terms of intra-site transitions, where the FeII centers in the low-spin state are independently photoexcited. The Franck-Condon state decays via the formation of a vibrationally hot high-spin (HS) state that displays coherent behavior within a few picoseconds and thermalizes within tens of picoseconds to yield a metastable HS state living for several hundreds of nanoseconds. Systematic comparison with the closely related mononuclear complex [Fe(terpy)2]2+ reveals that nuclearity has a profound impact on the photoinduced dynamics. More generally, this work provides guidelines for expanding the integration of oligonuclear complexes into new photoconversion schemes that may be triggered by ultrafast spin-switching.

Publisher's Note: Femtosecond X-Ray Scattering Study of Ultrafast Photoinduced Structural Dynamics in Solvated [Co(terpy)_{2}]

This corrects the article DOI: 10.1103/PhysRevLett.117.013002.

Modulating Charge-Carrier Dynamics in Mn-Doped All-Inorganic Halide Perovskite Quantum Dots through the Doping-Induced Deep Trap States.

Transition-metal ion doping has been demonstrated to be effective for tuning the photoluminescence properties of perovskite quantum dots (QDs). However, it would inevitably introduce defects in the lattice. As the Mn concentration increases, the Mn dopant photoluminescence quantum yield (PLQY) first increases and then decreases. Herein the influence of the dopant and the defect states on the photophysics in Mn-doped CsPbCl3 QDs was studied by time-resolved spectroscopies, whereas the energy levels of the possible defect states were analyzed by density functional theory calculations. We reveal the formation of deep interstitials defects (Cli) by Mn2+ doping. The depopulation of initial QD exciton states is a competition between exciton-dopant energy transfer and defect trapping on an early time scale (<100 ps), which determines the final PLQY of the QDs. The present work establishes a robust material optimization guideline for all of the emerging applications where a high PLQY is essential.

Revealing Hot and Long-Lived Metastable Spin States in the Photoinduced Switching of Solvated Metallogrid Complexes with Femtosecond Optical and X-ray Spectroscopies.

An atomistic understanding of the photoinduced spin-state switching (PSS) within polynuclear systems of d4-d7 transition metal ion complexes is required for their rational integration into light-driven reactions of chemical and biological interest. However, in contrast to mononuclear systems, the multidimensional dynamics of the PSS in solvated molecular arrays have not yet been elucidated due to the expected complications associated with the connectivity between the metal centers and the strong interactions with the surroundings. In this work, the PSS in a solvated triiron(II) metallogrid complex is characterized using transient optical absorption and X-ray emission spectroscopies on the femtosecond time scale. The complementary measurements reveal the photoinduced creation of energy-rich (hot) and long-lived quintet states, whose dynamics differ critically from their mononuclear congeners. This finding opens major prospects for developing novel schemes in solution-phase spin chemistry that are driven by the dynamic PSS process in compact oligometallic arrays.

Vibrational wavepacket dynamics in Fe carbene photosensitizer determined with femtosecond X-ray emission and scattering.

The non-equilibrium dynamics of electrons and nuclei govern the function of photoactive materials. Disentangling these dynamics remains a critical goal for understanding photoactive materials. Here we investigate the photoinduced dynamics of the [Fe(bmip)2]2+ photosensitizer, where bmip = 2,6-bis(3-methyl-imidazole-1-ylidine)-pyridine, with simultaneous femtosecond-resolution Fe Kα and Kß X-ray emission spectroscopy (XES) and X-ray solution scattering (XSS). This measurement shows temporal oscillations in the XES and XSS difference signals with the same 278 fs period oscillation. These oscillations originate from an Fe-ligand stretching vibrational wavepacket on a triplet metal-centered (3MC) excited state surface. This 3MC state is populated with a 110 fs time constant by 40% of the excited molecules while the rest relax to a 3MLCT excited state. The sensitivity of the Kα XES to molecular structure results from a 0.7% average Fe-ligand bond length shift between the 1 s and 2p core-ionized states surfaces.

Hot Branching Dynamics in a Light-Harvesting Iron Carbene Complex Revealed by Ultrafast X-ray Emission Spectroscopy.

Iron N-heterocyclic carbene (NHC) complexes have received a great deal of attention recently because of their growing potential as light sensitizers or photocatalysts. We present a sub-ps X-ray spectroscopy study of an FeII NHC complex that identifies and quantifies the states involved in the deactivation cascade after light absorption. Excited molecules relax back to the ground state along two pathways: After population of a hot 3 MLCT state, from the initially excited 1 MLCT state, 30 % of the molecules undergo ultrafast (150 fs) relaxation to the 3 MC state, in competition with vibrational relaxation and cooling to the relaxed 3 MLCT state. The relaxed 3 MLCT state then decays much more slowly (7.6 ps) to the 3 MC state. The 3 MC state is rapidly (2.2 ps) deactivated to the ground state. The 5 MC state is not involved in the deactivation pathway. The ultrafast partial deactivation of the 3 MLCT state constitutes a loss channel from the point of view of photochemical efficiency and highlights the necessity to screen transition-metal complexes for similar ultrafast decays to optimize photochemical performance.

Resolving the Ultrafast Changes of Chemically Inequivalent Metal-Ligand Bonds in Photoexcited Molecular Complexes with Transient X-ray Absorption Spectroscopy.

Photoactive transition-metal complexes that incorporate heteroleptic ligands present a first coordination shell, which is asymmetric. Although it is generally expected that the metal-ligand bond lengths respond differently to photoexcitation, resolving these fine structural changes remains experimentally challenging, especially for flexible multidentate ligands. In this work, ultrafast X-ray absorption spectroscopy is employed to capture directly the asymmetric elongations of chemically inequivalent metal-ligand bonds in the photoexcited spin-switching FeII complex [FeII(tpen)]2+ solvated in acetonitrile, where tpen denotes N,N,N',N'-tetrakis(2-pyridylmethyl)-1,2-ethylenediamine. The possibility to correlate precisely the nature of the donor/acceptor coordinating atoms to specific photoinduced structural changes within a binding motif will provide advanced diagnostics for optimizing numerous photoactive chemical and biological building blocks.

Finding intersections between electronic excited state potential energy surfaces with simultaneous ultrafast X-ray scattering and spectroscopy.

Light-driven molecular reactions are dictated by the excited state potential energy landscape, depending critically on the location of conical intersections and intersystem crossing points between potential surfaces where non-adiabatic effects govern transition probabilities between distinct electronic states. While ultrafast studies have provided significant insight into electronic excited state reaction dynamics, experimental approaches for identifying and characterizing intersections and seams between electronic states remain highly system dependent. Here we show that for 3d transition metal systems simultaneously recorded X-ray diffuse scattering and X-ray emission spectroscopy at sub-70 femtosecond time-resolution provide a solid experimental foundation for determining the mechanistic details of excited state reactions. In modeling the mechanistic information retrieved from such experiments, it becomes possible to identify the dominant trajectory followed during the excited state cascade and to determine the relevant loci of intersections between states. We illustrate our approach by explicitly mapping parts of the potential energy landscape dictating the light driven low-to-high spin-state transition (spin crossover) of [Fe(2,2'-bipyridine)3]2+, where the strongly coupled nuclear and electronic dynamics have been a source of interest and controversy. We anticipate that simultaneous X-ray diffuse scattering and X-ray emission spectroscopy will provide a valuable approach for mapping the reactive trajectories of light-triggered molecular systems involving 3d transition metals.

Asynchronous Photoexcited Electronic and Structural Relaxation in Lead-Free Perovskites.

Vacancy-ordered lead-free perovskites with more-stable crystalline structures have been intensively explored as the alternatives for resolving the toxic and long-term stability issues of lead halide perovskites (LHPs). The dispersive energy bands produced by the closely packed halide octahedral sublattice in these perovskites are meanwhile anticipated to facility the mobility of charge carriers. However, these perovskites suffer from unexpectedly poor charge carrier transport. To tackle this issue, we have employed the ultrafast, elemental-specific X-ray transient absorption (XTA) spectroscopy to directly probe the photoexcited electronic and structural dynamics of a prototypical vacancy-ordered lead-free perovskite (Cs3Bi2Br9). We have discovered that the photogenerated holes quickly self-trapped at Br centers, simultaneously distorting the local lattice structure, likely forming small polarons in the configuration of Vk center (Br2- dimer). More significantly, we have found a surprisingly long-lived, structural distorted state with a lifetime of ∼59 µs, which is ∼3 orders of magnitude slower than that of the charge carrier recombination. Such long-lived structural distortion may produce a transient "background" under continuous light illumination, influencing the charge carrier transport along the lattice framework.

Resonant Photoelectron Confinement in the SF6 Molecule.

Recent thorough experimental activity aiming to generate high harmonics in the SF6 molecules requires the knowledge of, on one hand, accurate valence-shell photoionization cross sections and phases, from a threshold up to a few tens of eV, where resonances are likely to appear, and, on the other hand, the effect of the nuclear vibrational dynamics on the process. In this work, we have experimentally determined and theoretically evaluated vibrationally resolved photoionization cross sections of SF6 up to 80 eV photon energies, with an emphasis on the E2T1u channel, for which vibrational progressions are fully resolved in the experiment. Our results reveal the presence of shape resonances due to excitation to SF6 virtual states lying just above the ionization threshold, in agreement with previous synchrotron radiation work and theoretical calculations. More interestingly, our calculations also disclose resonance features at photoelectron energies as high as 40-50 eV, which are due to the transient confinement of the ejected electron in the octahedral cage formed by the peripheral F atoms. In the vicinity of all resonances, including those due to confinement, the calculated ionization phases experience an excursion of about π or π/2 and significantly depend on the final vibrational state of the remaining cation. Both effects should be taken into account to correctly interpret ongoing high-harmonic generation work in SF6. A similar behavior is expected for other symmetric molecules containing a central atom, such as BF3, CF4, and the like.

Photostability and Photodegradation Processes in Colloidal CsPbI3 Perovskite Quantum Dots.

All-inorganic CsPbI3 perovskite quantum dots (QDs) have attracted intense attention for their successful application in photovoltaics (PVs) and optoelectronics that are enabled by their superior absorption capability and great photoluminescence (PL) properties. However, their photostability remains a practical bottleneck and further optimization is highly desirable. Here, we studied the photostability of as-obtained colloidal CsPbI3 QDs suspended in hexane. We found that light illumination does induce photodegradation of CsPbI3 QDs. Steady-state spectroscopy, X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, and transient absorption spectroscopy verified that light illumination leads to detachment of the capping agent, collapse of the CsPbI3 QD surface, and finally aggregation of surface Pb0. Both dangling bonds containing surface and Pb0 serve as trap states causing PL quenching with a dramatic decrease of PL quantum yield. Our work provides a detailed insight about the correlation between the structural and photophysical consequences of the photodegradation process in CsPbI3 QDs and may lead to the optimization of such QDs toward device applications.