Semiconductor mineral particles can act as photocatalysts for organic redox reactions that occur enzymatically in modern biological metabolic pathways. Semiconductor mineral-mediated photocatalysis may have contributed to the prebiotic synthesis of organic acids on the early Earth, but assessing the plausibility of this hypothesis is impeded by the lack of knowledge about the mechanisms for light-driven organic redox reactions on mineral surfaces. We selected one step in the reverse tricarboxylic acid (rTCA) cycle, the reduction of fumarate to succinate, that has been shown to be photocatalyzed by zinc sulfide (ZnS). Using static and time-resolved optical emission and absorption spectroscopy, we studied the adsorption of fumarate and the rates and pathways for charge transfer. We find that ZnS transfers photoexcited electrons to bound and dissolved fumarate on a wide range of time scales but not to succinate, supporting the concept that ZnS mediated photoreduction of fumarate could have operated in oceans of the early Earth. Optical transient absorption (TA) spectroscopy identified a signature tentatively attributed to the fumarate radical anion that is stable for at least 8 ns, providing evidence that fumarate photoreduction under solar illumination levels occurs by successive photoelectron transfer. The model for electronic excitation, relaxation, and interfacial charge-transfer processes in ZnS provided here will inform all future studies of the photochemical reactions of this mineral.

Photochemical oxidation of dissolved organic matter is a crucial component of carbon cycling in surface waters. Photo-oxidation of iron(III)-carboxylate complexes is of particular interest because complexation with iron(III) can sensitize this functional group to photodecarboxylation. The photo-oxidation mechanism of ferrioxalate has been extensively characterized, but it is unclear whether the mechanism or timing is similar for other more complex carboxylates. In this study, we use time-resolved infrared spectroscopy to demonstrate that Fe(III)-citrate, an aliphatic carboxylate, and Fe(III)-salicylate, an aromatic carboxylate, follow the same photo-oxidation kinetics as ferrioxalate. Hence the data suggest a common mechanism for decarboxylation of iron hydroxy carbonates. Differences in the CO₂ yield within 50 ps are qualitatively similar to the long-time-scale quantum yield for Fe(II) production.

Iron(III) oxalate, Fe3+(C2O4)33-, is a photoactive metal organic complex found in natural systems and used to quantify photon flux as a result of its high absorbance and reaction quantum yield. It also serves as a model complex to understand metal carboxylate complex photolysis because the mechanism of photolysis and eventual production of CO2 is not well understood for any system. We employed pump/probe mid-infrared transient absorption spectroscopy to study the photolysis reaction of the iron(III) oxalate ion in D2O and H2O up to 3 ns following photoexcitation. We find that intramolecular electron transfer from oxalate to iron occurs on a sub-picosecond time scale, creating iron(II) complexed by one oxidized and two spectator oxalate ligands. Within 40 ps following electron transfer, the oxidized oxalate molecule dissociates to form free solvated CO2(aq) and a species inferred to be CO2•- based on the appearance of a new vibrational absorption band and ab initio simulation. This work provides direct spectroscopic evidence for the first mechanistic steps in the photolysis reaction and presents a technique to analyze other environmentally relevant metal carboxylate photolysis reactions.

Semiconductors are commonly divided into materials with direct or indirect band gaps based on the relative positions of the top of the valence band and the bottom of the conduction band in crystal momentum (k) space. It has, however, been debated if k is a useful quantum number to describe the band structure in quantum-confined nanocrystalline systems, which blur the distinction between direct and indirect gap semiconductors. In bulk III-V semiconductor alloys like In1-xGaxP, the band structure can be tuned continuously from the direct- to indirect-gap by changing the value of x. The effect of strong quantum confinement on the direct-to-indirect transition in this system has yet to be established because high-quality colloidal nanocrystal samples have remained inaccessible. Herein, we report one of the first systematic studies of ternary III-V nanocrystals by utilizing an optimized molten-salt In-to-Ga cation exchange protocol to yield bright In1-xGaxP/ZnS core-shell particles with photoluminescence quantum yields exceeding 80%. We performed two-dimensional solid-state NMR studies to assess the alloy homogeneity and the extent of surface oxidation in In1-xGaxP cores. The radiative decay lifetime for In1-xGaxP/ZnS monotonically increases with higher gallium content. Transient absorption studies on In1-xGaxP/ZnS nanocrystals demonstrate signatures of direct- and indirect-like behavior based on the presence or absence, respectively, of excitonic bleach features. Atomistic electronic structure calculations based on the semi-empirical pseudopotential model are used to calculate absorption spectra and radiative lifetimes and evaluate band-edge degeneracy; the resulting calculated electronic properties are consistent with experimental observations. By studying photoluminescence characteristics at elevated temperatures, we demonstrate that a reduced lattice mismatch at the III-V/II-VI core-shell interface can enhance the thermal stability of emission. These insights establish cation exchange in molten inorganic salts as a viable synthetic route to nontoxic, high-quality In1-xGaxP/ZnS QD emitters with desirable optoelectronic properties.

A central goal of photoprotective energy dissipation processes is the regulation of singlet oxygen (¹O₂*) and reactive oxygen species in the photosynthetic apparatus. Despite the involvement of ¹O₂* in photodamage and cell signaling, few studies directly correlate ¹O₂* formation to nonphotochemical quenching (NPQ) or lack thereof. Here, we combine spin-trapping electron paramagnetic resonance (EPR) and time-resolved fluorescence spectroscopies to track in real time the involvement of ¹O₂* during photoprotection in plant thylakoid membranes. The EPR spin-trapping method for detection of ¹O₂* was first optimized for photosensitization in dye-based chemical systems and then used to establish methods for monitoring the temporal dynamics of ¹O₂* in chlorophyll-containing photosynthetic membranes. We find that the apparent ¹O₂* concentration in membranes changes throughout a 1 h period of continuous illumination. During an initial response to high light intensity, the concentration of ¹O₂* decreased in parallel with a decrease in the chlorophyll fluorescence lifetime via NPQ. Treatment of membranes with nigericin, an uncoupler of the transmembrane proton gradient, delayed the activation of NPQ and the associated quenching of ¹O₂* during high light. Upon saturation of NPQ, the concentration of ¹O₂* increased in both untreated and nigericin-treated membranes, reflecting the utility of excess energy dissipation in mitigating photooxidative stress in the short term (i.e., the initial ∼10 min of high light).

Organic-inorganic layered perovskites, or Ruddlesden-Popper perovskites, are two-dimensional quantum wells with layers of lead-halide octahedra stacked between organic ligand barriers. The combination of their dielectric confinement and ionic sublattice results in excitonic excitations with substantial binding energies that are strongly coupled to the surrounding soft, polar lattice. However, the ligand environment in layered perovskites can significantly alter their optical properties due to the complex dynamic disorder of the soft perovskite lattice. Here, we infer dynamic disorder through phonon dephasing lifetimes initiated by resonant impulsive stimulated Raman photoexcitation followed by transient absorption probing for a variety of ligand substitutions. We demonstrate that vibrational relaxation in layered perovskite formed from flexible alkyl-amines as organic barriers is fast and relatively independent of the lattice temperature. Relaxation in layered perovskites spaced by aromatic amines is slower, although still fast relative to bulk inorganic lead bromide lattices, with a rate that is temperature dependent. Using molecular dynamics simulations, we explain the fast rates of relaxation by quantifying the large anharmonic coupling of the optical modes with the ligand layers and rationalize the temperature independence due to their amorphous packing. This work provides a molecular and time-domain depiction of the relaxation of nascent optical excitations and opens opportunities to understand how they couple to the complex layered perovskite lattice, elucidating design principles for optoelectronic devices.