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Naphthalene diimide based diammonium cations can be utilized to produce 1D organic/inorganic metal halide semiconductors with internal charge separation via charge transfer states that lie energetically below the metal-halide excitonic absorption.
Colloidal quantum confined semiconductor-metal heterostructures are promising candidates for solar energy conversion because their light absorbing semiconductor and catalytic components can be independently tuned and optimized. Although the light-to-hydrogen efficiencies of such systems have shown interesting dependences on the morphologies of the semiconductor and metal domains, the mechanisms of such dependences are poorly understood. Here, we use Pt tipped 0D CdS quantum dots (with ∼4.6 nm diameter) and 1D CdS nanorods (of ∼13.8, 27.8, 66.6, and 88.9 nm average rod lengths) as a model system to study the distance-dependence of charge separation and charge recombination times and their impacts on photo-driven H2 production. The H2 generation quantum efficiency increases from 0.2% ± 0.0% in quantum dots to 28.9% ± 0.4% at a rod length of 28 nm and shows negligible changes at longer rod lengths. The half-life time of electron transfer from CdS to Pt increases monotonically with rod length, from 0.7 ± 0.1 in quantum dots to 170.2 ± 29.5 ps in the longest rods, corresponding to a slight decrease in electron transfer quantum efficiency from 92% to 81%. The amplitude-weighted average lifetime of charge recombination of the electron in Pt with the hole in CdS increases from 4.7 ± 0.4 µs in quantum dots to 149 ± 34 µs in 28 nm nanorods, and the lifetime does not increase further in longer rods, resembling the trend in the observed H2 generation quantum efficiency. Our result suggests that the competition of the charge recombination process with the hole removal by the sacrificial electron donor plays a dominant role in the observed nanorod length dependent overall light driven H2 generation quantum efficiency.
This award offset the registration and travel costs for researchers from U.S. institutions to attend the 32 nd Inter-American Photochemical Society meeting held on Jan 2-5, 2025, in Miramar Beach, Florida. The Inter-American Photochemical Society (I-APS) is a non-profit organization dedicated to promoting and disseminating knowledge and encouraging the development of fundamental and allied photochemistry throughout the Americas. The I-APS annual meeting is a particularly important tool for fulfilling this goal as it provides a welcoming venue to highlight research progress in theoretical, experimental, and applied aspects of photochemistry and molecular photophysics by researchers in all stages of their careers. The participation of graduate students and postdocs at this conference is particularly important as it aids in training the next generation of scientists in photochemistry. This award provided travel awards to three Assistant Professors and fourteen graduate and two undergraduate students to attend the I-APS Meeting in 2025. A majority of the science presented/discussed at the I-APS meeting is in direct alignment with the mission of the DOE and the Solar Photochemistry program, including studying fundamental phenomena, encompassing light absorption, photoinduced energy/electron transfer, charge separation, and charge and energy transport across mesoscale dimensions, as well as their application in generating electricity and chemical bonds using light.
This study explores how the quantum confined Stark effect (QCSE) influences minority carrier lifetimes in III-N quantum wells (QWs) by varying the well width. It is found that increasing QW width from zero (bulk material) increases radiative lifetime due to charge separation until charge screening effects reduce and rectify the QCSE for large well widths.
Photosystem I (PSI) uses an antenna of chlorophyll (Chl) molecules to create a charge separated state with high quantum efficiency. Understanding the charge separation mechanism is currently hindered by spectral overlap between the antenna and reaction center (RC) Chls and the fact that energy transfer and electron transfer occur with similar time scales. Here, we characterize the antenna excited states by applying two-dimensional electronic (2DES) and two-dimensional electronic-vibrational (2DEV) spectroscopy to PSI complexes with closed RCs. Comparison of the 2DES and 2DEV spectra, which evolve with the same kinetics, enabled characterization of the vibrational modes of the antenna during energy equilibration between spectrally distinct Chls. Through global analysis, we learn how energy transfer between the Bulk and Red Chls presents in the 2DEV spectra and we definitively identify vibrations of the cationic components of the mixed exciton and intermolecular charge transfer states associated with the Red Chls. This work enables future studies of the initial charge separation mechanism of PSI by 2DEV spectroscopy.
Multiferroic BiFeO3 (BFO) films with spontaneously formed periodic stripe domains can generate above-gap open circuit voltages under visible light illumination; nevertheless the underlying mechanism behind this intriguing optoelectronic response has not been understood to date. Here, we make contact-free measurements of light-induced currents in epitaxial BFO films via detecting terahertz radiation emanated by these currents, enabling a direct probe of the intrinsic charge separation mechanisms along with quantitative measurements of the current amplitudes and their directions. In the periodic stripe samples, we find that the net photocurrent is dominated by the charge separation across the domain walls, whereas in the monodomain samples the photovoltaic response arises from a bulk shift current associated with the non-centrosymmetry of the crystal. The peak current amplitude driven by the charge separation at the domain walls is found to be 2 orders of magnitude higher than the bulk shift current response, indicating the prominent role of domain walls acting as nanoscale junctions to efficiently separate photogenerated charges in the stripe domain BFO films. These findings show that domain-wall-engineered BFO thin films offer exciting prospects for ferroelectric-based optoelectronics, as well as bias-free strong terahertz emitters.
Abstract Natural photosynthetic protein complexes capture sunlight to power the energetic catalysis that supports life on Earth. Yet these natural protein structures carry an evolutionary legacy of complexity and fragility that encumbers protein reengineering efforts and obfuscates the underlying design rules for light-driven charge separation. De novo development of a simplified photosynthetic reaction center protein can clarify practical engineering principles needed to build new enzymes for efficient solar-to-fuel energy conversion. Here, we report the rational design, X-ray crystal structure, and electron transfer activity of a multi-cofactor protein that incorporates essential elements of photosynthetic reaction centers. This highly stable, modular artificial protein framework can be reconstituted in vitro with interchangeable redox centers for nanometer-scale photochemical charge separation. Transient absorption spectroscopy demonstrates Photosystem II-like tyrosine and metal cluster oxidation, and we measure charge separation lifetimes exceeding 100 ms, ideal for light-activated catalysis. This de novo-designed reaction center builds upon engineering guidelines established for charge separation in earlier synthetic photochemical triads and modified natural proteins, and it shows how synthetic biology may lead to a new generation of genetically encoded, light-powered catalysts for solar fuel production.
We report solar-to-fuel conversion reaction often requires multiple proton-coupled electron transfer (PCET) processes powered by the energetic electrons and/or holes generated by the absorption of multiple photons. The effective coupling of multiple electron transfer from the light absorber with the multiple PCET reactions at the catalytic center is one of the key challenges in efficient and selective conversion of solar energy to chemical fuels. In this paper, we examine the dynamics of multiple electron transfer in quantum confined CdS nanorods with a Pt tip, in which the CdS rod functions as the light absorber and the Pt tip the catalytic center. By excitation-fluence-dependent transient absorption spectroscopic measurements, we show that the multiexciton Auger recombination rate in CdS rods follows a carrier-collision model, k n A = n 2 (n – 1)/4k 2 A , with a biexciton lifetime (1/k 2 A ) of 2.0 ± 0.2 ns. In CdS–Pt nanorods, electron transfer kinetics from the CdS conduction band edge to the Pt show negligible dependence on the excitation fluence, occurring with a half-life time of 5.6 ± 0.6 ps. The efficiency of multiple exciton dissociation by multiple electron transfer to Pt decreases from 100% in biexciton states to ~41% at 22 exciton state due to the competition with Auger recombination. The half-lifetime of the n-charge separated state recombination (with n electrons in the Pt and n holes in the CdS) decreases from 10 μs in the single charge separated state to 42 ns in nine charge separated states. Our findings suggest the possibility of driving multielectron photocatalytic reactions under intense illumination and controlling product selectivity through multielectron transfer.
Controlling charge transport at the interfaces of nanostructures is crucial for their successful use in optoelectronic and solar energy applications. Mixed-dimensional heterostructures based on single-walled carbon nanotubes (SWCNTs) and transition metal dichalcogenides (TMDCs) have demonstrated exceptionally long-lived charge-separated states. However, the factors that control the charge transport at these interfaces remain unclear. In this study, we directly image charge transport at the interfaces of single- and multilayered MoS 2 and (6,5) SWCNT heterostructures using transient absorption microscopy. We find that charge recombination becomes slower as the layer thickness of MoS 2 increases. This behavior can be explained by electron delocalization in multilayers and reduced orbital overlap with the SWCNTs, as suggested by nonadiabatic (NA) molecular dynamics (MD) simulations. Dipolar repulsion of interfacial excitons results in rapid density-dependent transport within the first 100 ps. Stronger repulsion and longer-range charge transport are observed in heterostructures with thicker MoS 2 layers, driven by electron delocalization and larger interfacial dipole moments. These findings are consistent with the results from NAMD simulations. Our results suggest that heterostructures with multilayer MoS 2 can facilitate long-lived charge separation and transport, which is promising for applications in photovoltaics and photocatalysis.
Understanding how short-range electron transfer generates photocurrent in organic solar cells and what photochemical driving force is needed to maximize efficiencies has been an immensely difficult problem. Here we show how these questions are intertwined: the driving force controls the average charge-transfer distance, skipping the shortest-range states in the optimal case. Using photoinduced absorption-detected magnetic resonance, we measure average charge-separation distances in dilute donor–acceptor blends as a function of driving force, and compare these with free charge yields measured by time-resolved microwave conductivity. We find that the largest driving forces show the shortest charge-separation distances, explaining their suppressed free-carrier generation. These results support a long-range electron-transfer model, wherein the driving force controls the initial delocalization of the electron–hole pair. The minimum driving force required for efficient charge separation (and minimal voltage losses) is ultimately set by the dielectric constant of the material.
The chiral magnetic effect (CME) refers to charge separation along a strong magnetic field due to imbalanced chirality of quarks in local parity and charge-parity violating domains in quantum chromodynamics. The experimental measurement of the charge separation is made difficult by the presence of a major background from elliptic azimuthal anisotropy. This background and the CME signal have different sensitivities to the spectator and participant planes, and could thus be determined by measurements with respect to these planes. We report such measurements in Au+Au collisions at a nucleon-nucleon center-of-mass energy of 200 GeV at the Relativistic Heavy-Ion Collider. It is found that the charge separation, with the flow background removed, is consistent with zero in peripheral (large impact parameter) collisions. Some indication of finite CME signals is seen with a significance of 1–3 standard deviations in mid-central (intermediate impact parameter) collisions. Furthermore, significant residual background effects may, however, still be present.
Solar fuels catalysis is a promising route to efficiently harvesting, storing, and utilizing abundant solar energy. To achieve this promise, however, molecular systems must be designed with sustainable components that can balance numerous photophysical and chemical processes. To that end, here we report on the structural and photophysical characterization of a series of Cu(I)–anthraquinone-based electron donor–acceptor dyads. The dyads utilized a heteroleptic Cu(I) bis-diimine architecture with a copper(I) bis-phenanthroline chromophore donor and anthraquinone electron acceptor. We characterized the structures of the complexes using x-ray crystallography and density functional theory calculations and the photophysical properties via resonance Raman and optical transient absorption spectroscopy. The calculations and resonance Raman spectroscopy revealed that excitation of the Cu(I) metal-to-ligand charge-transfer (MLCT) transition transfers the electron to a delocalized ligand orbital. The optical transient absorption spectroscopy demonstrated that each dyad formed the oxidized copper–reduced anthraquinone charge-separated state. Unlike most Cu(I) bis-phenanthroline complexes where increasingly bulky substituents on the phenanthroline ligands lead to longer MLCT excited-state lifetimes, here, we observe a decrease in the long-lived charge-separated state lifetime with increasing steric bulk. The charge-separated state lifetimes were best explained in the context of electron-transfer theory rather than with the energy gap law, which is typical for MLCT excited states, despite the complete conjugation between the phenanthroline and anthraquinone moieties.
Proton-coupled electron transfer (PCET) reactions mediate essential biological energy-conversion processes, yet dynamical experiments that distinguish concerted electron/proton motion from sequential electron-transfer/proton-transfer pathways are unprecedented on ultrafast time scales. Here we report a tightly coupled donor–spacer–acceptor assembly, NDI-Sp-PhOH/BI, that enables direct interrogation of light-triggered and ultrafast PCET dynamics. Photoexcitation of the naphthalene diimide chromophore drives charge separation forming NDI radical anion and benzimidazolium phenoxy radical (PhO●/BIH+) products with a 440 fs time constant, followed by thermal charge recombination on a 5 ps time scale. Transient visible/near-infrared and mid-infrared spectroscopies independently track electron and proton motion and reveal coincident formation and decay of the charge-separated PCET products, excluding detectable phenol radical cation or phenoxide intermediates expected for sequential electron transfer-proton transfer (ET-PT) pathways. Surface-hopping quasiclassical trajectory simulations demonstrate rapid proton relocation coupled to evolution from locally excited to charge-transfer states, congruent with a concerted mechanism. These combined spectroscopic and computational results establish NDI-Sp-PhOH/BI as an archetype for ultrafast, concerted PCET occurring with unit quantum yield; further, because this platform provides distinct electronic and vibrational spectroscopic handles in its ground, electronically excited, and charge-separated states, it provides new opportunities to characterize mechanistic crossover in biomimetic PCET systems.
This project was motivated by an overarching goal to elucidate the mechanism of energy and electron transfer that governs the efficient charge separation in photosystem I (PSI) complexes. PSI is a natural light harvesting complex that drives oxygenic photosynthesis in plants, algae, and cyanobacteria. It uses ~300 tightly packed chlorophylls (Chls) to absorb photons, transfer the excitation energy to the reaction center (RC), and generate a charge separated state with near unity quantum efficiency (QE). A better understanding of the mechanism of energy transfer and charge separation in PSI is required for understanding the high QE of natural light harvesting complexes, and it could lead to the further development of artificial photosynthetic systems for solar energy conversion and modification of light harvesting complexes to improve crop yields. We applied two-dimensional optical spectroscopies to different cyanobacterial photosystem I complexes, including PSI complexes that contain Chl f molecules, to map energy transfer pathways and gain insight into the efficient light harvesting of PSI. We used two-dimensional electronic spectroscopies (2DES) to map energy transfer in Chl a and Chl f containing PSI complexes. To investigate the Chl f PSI complexes, we modified our spectrometer to probe the lower energy states associated with Chl f molecules. We interpreted the 2DES spectra through global analysis procedures to generate maps of energy transfer. We also constructed a two-dimensional electronic vibrational (2DEV) spectrometer that will be used to investigate charge transfer transitions and dynamics within PSI complexes. Measurements were performed on model systems to establish general data analysis procedures for interpreting 2D spectra and gain insight into protein cofactor interactions.
This project was motivated by an overarching goal to elucidate the mechanism of energy and electron transfer that governs the efficient charge separation in photosystem I (PSI) complexes. PSI is a natural light harvesting complex that drives oxygenic photosynthesis in plants, algae, and cyanobacteria. It uses ~300 tightly packed chlorophylls (Chls) to absorb photons, transfer the excitation energy to the reaction center (RC), and generate a charge separated state with near unity quantum efficiency (QE). A better understanding of the mechanism of energy transfer and charge separation in PSI is required for understanding the high QE of natural light harvesting complexes, and it could lead to the further development of artificial photosynthetic systems for solar energy conversion. We applied two-dimensional electronic spectroscopy (2DES) to different cyanobacterial photosystem I complexes to map energy transfer pathways to gain insight into the efficient light harvesting of PSI. We interpreted the 2DES spectra through a global analysis procedure, finding two ultrafast equilibration processes involving red-shifted Chl states. The analysis procedure is general and can be readily applied to other natural and artificial light harvesting systems. In addition to investigating PSI complexes, we also performed measurements on model systems to establish general data analysis procedures for interpreting 2D spectra.
Highly concentrated solutions of chlorophyll display rapid fluorescence quenching. The same devastating energy loss is not seen in photosynthetic light-harvesting antenna complexes, despite the need for chromophores to be in close proximity to facilitate energy transfer. A promising, though unconfirmed mechanism for the observed quenching is energy transfer from an excited chlorophyll monomer to a closely associated chlorophyll pair that subsequently undergoes rapid nonradiative decay to the ground state via a short-lived intermediate charge-transfer state. In this work, we make use of newly emerging fast methods in quantum chemistry to assess the feasibility of this proposed mechanism. We calculate rate constants for the initial charge separation, based on Marcus free-energy surfaces extracted from molecular dynamics simulations of solvated chlorophyll pairs, demonstrating that this pathway will compete with fluorescence (i.e., drive quenching) at experimentally measured quenching concentrations. We show that the rate of charge separation is highly sensitive to interchlorophyll distance and the relative orientations of chromophores within a quenching pair. We discuss possible solvent effects on the rate of charge separation (and consequently the degree of quenching), using the light-harvesting complex II (LH2) protein from rps. acidophila as a specific example of how this process might be controlled in a protein environment. Crucially, we reveal that the LH2 antenna protein prevents quenching, even at the high chlorophyll concentrations required for efficient energy transfer, by restricting the range of orientations that neighboring chlorophyll pairs can adopt.
Photosynthetic integral membrane reaction center (RC) proteins capture and convert sunlight into chemical energy via efficient charge separation achieved through a series of rapid, photoinitiated electron transfer steps. These fast electron transfers create an entangled spin qubit (radical) pair that contains detailed information about the weak magnetic interactions, structure, and dynamics of localized protein environments involved in charge separation events. In this work, we investigate how these entangled electron spin qubits interact with nuclear spins of the protein environment using the high spectral resolution of 130 GHz electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR). Spectroscopic interrogation enabled the observation and probing of protons located in the electron transfer pathway between the membrane-spanning electron pair P + Q A - (where P + is the primary donor, a special pair of bacteriochlorophylls, and Q A is the primary quinone acceptor) in the bacterial RC. Spectroscopic analysis reveals hydrogen-bonding interactions involved in regulating the route that light-induced electrons travel through the RC protein during charge separation.
Organic molecules and quantum dots (QDs) have both shown promise as materials that can host quantum bits (qubits). This is in part because of their synthetic tunability. The current work employs a combination of both materials to demonstrate a series of tunable quantum dot–organic molecule conjugates that can both host photogenerated spin-based qubit pairs (SQPs) and sensitize molecular triplet states. The photogenerated qubit pairs, composed of a spin-correlated radical pair (SCRP), are particularly intriguing since they can be initialized in well-defined, nonthermally populated, quantum states. Additionally, the radical pair enables charge recombination to a polarized molecular triplet state, also in a well-defined quantum state. The materials underlying this system are an organic molecular chromophore and electron donor, 9,10-bis(phenylethynyl)anthracene, and a quantum dot acceptor composed of ZnO. We prepare a series of quantum dot–molecule conjugates that possess variable quantum dot size and two different linker lengths connecting the two moieties. Optical spectroscopy revealed that the QD–molecule conjugates undergo photoexcited charge separation to generate long-lived charge-separated radical pairs. The resulting spin states are probed using light-induced time-resolved electron paramagnetic resonance (TR-EPR) spectroscopy, revealing the presence of singlet-generated SCRPs and molecular triplet states. Notably, the EPR spectra of the radical pairs are dependent on the geometry of this highly tunable system. The g value of the ZnO QD anion is size tunable, and the line widths are influenced by radical pair separation. Overall, this work demonstrates the power of synthetic tunability in adjusting the spin specific addressability, satisfying a key requirement of functional qubit systems.