Photoinduced Dynamics Research Articles

Modeling of Nonlinear Optical Phenomena in Host-Guest Systems Using Bond Fluctuation Monte Carlo Model: A Review.

We review the results of Monte Carlo studies of chosen nonlinear optical effects in host-guest systems, using methods based on the bond-fluctuation model (BFM) for a polymer matrix. In particular, we simulate the inscription of various types of diffraction gratings in degenerate two wave mixing (DTWM) experiments (surface relief gratings (SRG), gratings in polymers doped with azo-dye molecules and gratings in biopolymers), poling effects (electric field poling of dipolar molecules and all-optical poling) and photomechanical effect. All these processes are characterized in terms of parameters measured in experiments, such as diffraction efficiency, nonlinear susceptibilities, density profiles or loading parameters. Local free volume in the BFM matrix, characterized by probabilistic distributions and correlation functions, displays a complex mosaic-like structure of scale-free clusters, which are thought to be responsible for heterogeneous dynamics of nonlinear optical processes. The photoinduced dynamics of single azopolymer chains, studied in two and three dimensions, displays complex sub-diffusive, diffusive and super-diffusive dynamical regimes. A directly related mathematical model of SRG inscription, based on the continuous time random walk (CTRW) formalism, is formulated and studied. Theoretical part of the review is devoted to the justification of the a priori assumptions made in the BFM modeling of photoinduced motion of the azo-polymer chains.

Linear-Response and Nonlinear-Response Formulations of the Instantaneous Marcus Theory for Nonequilibrium Photoinduced Charge Transfer.

Instantaneous Marcus theory (IMT) offers a way for capturing the time-dependent charge transfer (CT) rate coefficient in nonequilibrium photoinduced CT processes, where the system was photoexcited from its equilibrated ground state vertically to the excitonic state, followed by an electronic transition to the CT state. As derived from the linearized semiclassical nonequilibrium Fermi's golden rule (LSC NE-FGR), the original IMT requires expensive all-atom nonequilibrium molecular dynamics (NEMD) simulations. In this work, we propose computationally efficient linear-response and nonlinear-response formulations for IMT rate calculations, which only require equilibrium molecular dynamics simulations. The linear- and nonlinear-response IMT methods were tested to predict the transient behavior in the photoinduced CT dynamics of the carotenoid-porphyrin-C60 molecular triad solvated in explicit tetrahydrofuran. Our result demonstrated that the nonlinear-response IMT is in excellent agreement with the benchmark NEMD for all cases investigated here, whereas the linear-response IMT predicts the correct trend for all cases but overestimates the transient CT rate in one case involving a significant nonequilibrium relaxation. This mild breakdown of linear-response IMT is due to neglecting the higher-order terms in the exact nonlinear-response IMT. Taking advantage of time translational symmetry, the linear- and nonlinear-response approaches were demonstrated to be able to reduce the computational cost by 80% and 60% compared with NEMD simulations, respectively. Thus, we highly recommend the readily applicable and accurate nonlinear-response IMT approach for simulating nonequilibrium CT processes in complex molecular systems in the condensed phase.

Photoinduced intramolecular charge transfer and relaxation dynamics of 4-dimethylaminopyridine in water, alcohols, and aprotic solvents

4-Dimethylaminopyridine (1), a charge-transfer (CT) probe and strong acceptor of proton and hydrogen bond, has been studied by stationary and broadband transient absorption (TA) spectroscopy. Upon photoexcitation S0→S1°, intramolecular CT occurs only in polar solvents suggesting the CT is solvent- and solvation-controlled. In n-hexane, there is no CT the state S1° decays with 81 ps directly to ground state S0. In aprotic acetonitrile, charge transfer S1°→S1n develops with 16 ps (n indicates non-protonated 1), much slower than solvation, implying a reaction barrier of 12 kJ/mol. Subsequently S1n decays to S0 on a 10 ns time scale with a large triplet yield. In water, 1 is fully protonated at the pyridine nitrogen, the charge transfer S1°→S1p (p indicates protonation) proceeds nearly barrierless with 0.15 ps, followed by a biexponential evolution with 2.6 (55 %) and 26 ps. The behavior in primary alcohols, from methanol to n-octanol in decreasing acidity, show mixed features characteristic for both acetonitrile and water, suggesting the presence of non-protonated and protonated species in solution. Decomposed emission spectra in n-propanol and n-butanol provide an estimate of the excited-state basicity, pKa ∼20, much higher than pKa = 9.3 in S0. The stationary spectra in alcohols originate both from protonated and non-protonated species. They can be well modelled by the spectra in water/acetonitrile mixture with varying water content, however differently for absorption and emission. In moderately acidic methanol, the emission spectra are very similar to those in water, while in very weakly acidic n-octanol or tert-butanol they resemble more those in acetonitrile. This picture is corroborated by transient absorption spectra and kinetics in the alcohols and water/acetonitrile mixtures. Deviations from the model, such as possible contribution from additional emission bands, are discussed.

Finite-element simulation of photoinduced strain dynamics in silicon thin plates.

In this paper, we investigate the femtosecond-optical-pulse-induced strain dynamics in relatively thin (100 nm) and thick (10 000 nm) silicon plates based on finite-element simulations. In the thin sample, almost spatially homogeneous excitation by the optical pulse predominantly generates a standing wave of the lowest-order acoustic resonance mode along the out-of-plane direction. At the same time, laterally propagating plate waves are emitted at the sample edge through the open edge deformation. Fourier transformation analysis reveals that the plate waves in the thin sample are mainly composed of two symmetric Lamb waves, reflecting the spatially uniform photoexcitation. In the thick sample, on the other hand, only the near surface region is photo-excited and thus a strain pulse that propagates along the out-of-plane direction is generated, accompanying the laterally propagating pulse-like strain dynamics through the edge deformation. These lateral strain pulses consist of multiple Lamb waves, including asymmetric and higher-order symmetric modes. Our simulations quantitatively demonstrate the out-of-plane and in-plane photoinduced strain dynamics in realistic silicon plates, ranging from the plate wave form to pulse trains, depending on material parameters such as sample thickness, optical penetration depth, and sound velocity.

Ultrafast dynamics of photoexcited carriers in perovskite semiconductor nanocrystals

Abstract Perovskite semiconductor nanocrystals have emerged as a promising family of materials for optoelectronic applications including light-emitting diodes, lasers, light-to-electricity convertors and quantum light emitters. The performances of these devices are fundamentally dependent on different aspects of the excited-state dynamics in nanocrystals. Herein, we summarize the recent progress on the photoinduced carrier dynamics studied by a variety of time-resolved spectroscopic methods in perovskite nanocrystals. We review the dynamics of carrier generation, recombination and transport under different excitation densities and photon energies to show the pathways that underpin the photophysics for light-emitting diodes and solar cells. Then, we highlight the up-to-date spin dynamics and coherent exciton dynamics being manifested with the exciton fine levels in perovskite semiconductor nanocrystals which are essential for potential applications in quantum information technology. We also discuss the controversial results and the possible origins yet to be resolved. In-depth study toward a comprehensive picture of the excited-state dynamics in perovskite nanocrystals may provide the key knowledge of the device operation mechanism, enlighten the direction for device optimization and stimulate the adventure of new conceptual devices.

Electron-Nuclear Dynamics Accompanying Proton-Coupled Electron Transfer.

Although photoinduced proton-coupled electron transfer (PCET) plays an essential role in photosynthesis, a full understanding of the mechanism is still lacking due to the complex nonequilibrium dynamics arising from the strongly coupled electronic and nuclear degrees of freedom. Here we report the photoinduced PCET dynamics of a biomimetic model system investigated by means of transient IR and two-dimensional electronic-vibrational (2DEV) spectroscopies, IR spectroelectrochemistry (IRSEC), and calculations utilizing long-range-corrected hybrid density functionals. This collective experimental and theoretical effort provides a nuanced picture of the complicated dynamics and synergistic motions involved in photoinduced PCET. In particular, the evolution of the 2DEV line shape, which is highly sensitive to the mixing of vibronic states, is interpreted by accurate computational modeling of the charge separated state and is shown to represent a gradual change in electron density distribution associated with a dihedral twist that occurs on a 120 fs time scale.

Photochemical synthesis of Ni-Ni(OH)2 synergistic cocatalysts hybridized with CdS nanorods for efficient photocatalytic hydrogen evolution

Ni-Ni(OH)2 composite was synthesized by a novel and facile photodeposition strategy and used as the cocatalyst of CdS for solar-to-hydrogen conversion. Under visible light, the hydrogen evolution rate of Ni-Ni(OH)2/CdS was 428 mmol g−1h−1 and remained essentially unchanged after 24 h in Na2S/Na2SO3 aqueous solution. In particular, the Ni-Ni(OH)2/CdS also displayed excellent photocatalytic hydrogen evolution reaction (HER) activity (13.3 mmol g−1h−1) in 40 vol% glycerol. A set of spectroscopy and electrochemical characterizations were performed to explore the photoinduced interfacial charge dynamics. Ni and Ni(OH)2 were synergistic cocatalysts for improving charge utilization and photocatalytic performance.

Site-Specific Photoinduced Dynamics of the LOV Protein EL222 Monitored by Multiple Genetically Encoded Infrared Probes

Proteins containing the light-oxygen-voltage (LOV) domain are photosensory receptors that mediate biological actions in response to blue light. For instance, the bacterial transcription factor EL222 regulates gene expression in a light-regulated manner and has found use in optogenetic applications. Upon excitation of the embedded flavin mononucleotide (FMN) cofactor, EL222 undergoes structural changes that ultimately drive its association with DNA. However, our knowledge of the light-adapted state(s) and the molecular mechanism underlying the transition between dark and lit states is incomplete.

Coordination-Driven Enhancement of Radiosensitization by Black Phosphorus via Regulating Tumor Metabolism.

Coordination-driven surface modification is an effective strategy to achieve nanosystem functionalization and improved physicochemical performance. Black phosphorus (BP)-based nanomaterials demonstrate great potential in cancer therapy, but their poor stability, low X-ray mass attenuation coefficient, and nonselectivity limit the application in radiotherapy. Herein, we used unsaturated iridium complex to coordinate with BP nanosheets to synthesize a two-dimensional layered nanosystem (RGD-Ir@BP) with higher biostability. Ir complex improves the photoelectric properties and photoinduced charge carrier dynamics of BP, hence Ir@BP generated more singlet oxygen after X-ray irradiation. In in vivo experiments, with X-ray irradiation, RGD-Ir@BP effectively inhibited nasopharyngeal carcinoma tumor growth but with minor side effects. Additionally, based on untargeted metabolomics analysis, the combined treatment specifically down-regulated the tumor proliferative mark of prostaglandin E2 in cancer cells. In general, this study provides a design strategy of high-performance coordination-driven BP-based nanosensitizer in cancer radiotherapy.

Intraband dynamics and exciton trapping in the LH2 complex of Rhodopseudomonas acidophila.

Over the last several decades, the light-harvesting protein complexes of purple bacteria have been among the most popular model systems for energy transport in excitonic systems in the weak and intermediate intermolecular coupling regime. Despite this extensive body of scientific work, significant questions regarding the excitonic states and the photo-induced dynamics remain. Here, we address the low-temperature electronic structure and excitation dynamics in the light-harvesting complex 2 of Rhodopseudomonas acidophila by two-dimensional electronic spectroscopy. We find that, although at cryogenic temperature energy relaxation is very rapid, exciton mobility is limited over a significant range of excitation energies. This points to the presence of a sub-200 fs, spatially local energy-relaxation mechanism and suggests that local trapping might contribute substantially more in cryogenic experiments than under physiological conditions where the thermal energy is comparable to or larger than the static disorder.

Excitation Wavelength‐Dependent Charge Generation Dynamics in a Nonfullerene Organic Solar Cell Interface

Unraveling the charge generation dynamics at the donor–acceptor (D−A) interfaces is crucial for improving the photovoltaic performances of nonfullerene acceptor‐based organic solar cells (OSCs). Herein, time‐dependent density functional theory (TDDFT) based nonadiabatic dynamics simulations are used to explore the ultrafast photoinduced dynamics at a nonfullerene D–A PTB7@PDI interface. Based on the results, it is found that such an interface exhibits distinct charge generation processes upon excitation with different wavelengths. The excitation at ≈591 nm mainly results in the local exciton |PTB7∗>, whereas the charge transfer exciton |PTB7+PDI−> also has minor contribution. Later on, the electron transfer from PTB7 to PDI, i.e., channel I charge generation process, occurs in 1 ps. The situations are much more complex when the excitation is conducted using ≈487 nm light. The initial populated excitons include local excitons |PDI∗>, |PTB7∗>, and charge transfer exciton |PTB7+PDI−>, after which both channel I and channel II charge generation take place ultrafast. However, in both situations, the charge generation processes occur within a few picoseconds, which is consistent with previous experimental work. Such ultrafast charge generation processes in a wide range of solar spectra are one of the reasons responsible for the excellent photovoltaic properties of such OSCs.

Engineering couplings for exciton transport using synthetic DNA scaffolds

Summary Control over excitons enables electronic energy to be harnessed and transported for light harvesting and molecular electronics. Such control requires nanoscale precision over the molecular components. Natural light-harvesting systems achieve this precision through sophisticated protein machinery, which is challenging to replicate synthetically. Here, we introduce a DNA-based platform that spatially organizes cyanine chromophores to construct tunable excitonic systems. We synthesized DNA-chromophore nanostructures and characterized them with ensemble ultrafast and single-molecule spectroscopy and structure-based modeling. This synthetic approach facilitated independent control over the coupling among the chromophores and between the chromophores and the environment. We demonstrated that the coupling between the chromophores and the environment could enhance exciton transport efficiency, highlighting the key role of the environment in driving exciton dynamics. Control over excitons, as reported here, offers a path toward the development of designer nanophotonic devices.

1T-Rich 2D-WS2 as an interfacial agent to escalate photo-induced charge transfer dynamics in dopant-free perovskite solar cells

The deficiency in the photo-induced charge transfer dynamics at the perovskite-charge transport layer interfaces due to depleted energy alignment and surface traps impedes perovskite solar cells performance improvement. Herein, we suggest a simplistic interfacial engineering protocol to overcome current challenges.

Site-dependent photoinduced charge carrier dynamics in nitrogen/fluorine doped TiO2 nanoparticles

Electron and hole trapping/recombination dynamics in N-doped and F-doped TiO2 nanoparticles.

New theoretical insights into the photoinduced carrier transfer dynamics in WS2/WSe2 van der Waals heterostructures.

Shedding light on the dynamics of charge transfer is fundamental and important to understand the light-photocurrent power conversion in transition-metal dichalcogenide (TMD) heterostructures. Herein, based on time-dependent ab initio nonadiabatic molecular dynamics simulation, we studied the photoinduced carrier transfer dynamics in the WS2/WSe2 heterostructure and further analyzed the effects of stacking configuration and temperature. Our calculations show that the time scales of ultrafast hole transfer in the C7 and T stacking configurations are 35 fs and 30 fs, respectively, which are mainly caused by the adiabatic charge transfer mechanism. Meanwhile, the time scales of ultrafast electron transfer in the C7 and T stacking configurations are 12 fs and 40 fs, respectively, which are in good agreement with the experimental result. We also investigated in detail the photoinduced carrier transfer pathways of C7 and T stacking configurations, which appear to have some significant differences. In addition, we found that the temperature basically has no effect on the electron transfer dynamics of the WS2/WSe2 heterostructure; this is in excellent agreement with the experimental observation. In short, the reported findings can provide more in-depth insights into the photoinduced carrier transfer dynamics of TMD-based van der Waals heterostructures.

Ultrafast "end-on"-to-"side-on" binding-mode isomerization of an iron-carbon dioxide complex.

Carbon dioxide (CO2) binding by transition metals is a captivating phenomenon with a tremendous impact in environmental science and technology, most notably, for establishing circular economies based on greenhouse gas emissions. The molecular and electronic structures of coordination compounds containing CO2 can be studied in great detail using photochemical precursors bearing the photolabile oxalato-ligand. Here, we study the photoinduced elementary dynamics of the ferric complex, [FeIII(cyclam)(C2O4)]+, in dimethyl sulfoxide solution using femtosecond mid-infrared spectroscopy following oxalate-to-iron charge transfer excitation with 266 nm pulses. The pump-probe response in the ν3-region of carbon dioxide gives unequivocal evidence that a CO2-molecule is detached from the metal within only 500 fs and with a primary quantum yield of 38%. Simultaneously, a primary ferrous product is formed that carries a carbon dioxide radical anion ligand absorbing at 1649 cm-1, which is linked to the metal in a bent-O-"end-on" fashion. This primary ηO,bent1-product is formed with substantial excess vibrational energy, which relaxes on a time scale of several picoseconds. Prior to full thermalization, however, a fraction of the ferrous primary product can structurally isomerize at a rate of 1/(3.5 ps) to a secondary ηCO2-product absorbing at 1727 cm-1, which features a bent carbon dioxide ligand that is linked to the metal in a "side-on" fashion. The ηO,bent1-to-ηCO2 isomerization requires an intersystem crossing from the sextet to the quartet state, which rationalizes a partial trapping of the system in the metastable bent-O-"end-on" geometry. Finally, a fraction (62%) of the initially photoexcited complexes can return without structural changes to the parent's electronic ground state, but dressed with excess kinetic energy, which relaxes again on a time scale of several picoseconds.

Interfacial photoinduced carrier dynamics tuned by polymerization of coronene molecules encapsulated in carbon nanotubes: bridging type-I and type-II heterojunctions.

Carbon nanomaterials play important roles in modern scientific research. Integrating different carbon-based building blocks into nano-hybrid architectures not only takes full advantage of each component, but also brings in novel interfacial properties. Herein, we have employed density functional theory (DFT) calculations to investigate the effects of polymerization degree of coronene molecules encapsulated in single-walled carbon nanotubes (SWNTs) (19,0) on their interfacial properties. The present results reveal that the interfacial properties of the formed heterojunctions are remarkably regulated by the polymerization degree. For example, monomer- and dimer-encapsulated SWNTs are type-I heterojunctions in which interfacial excitation energy transfer is preferred, whereas interfacial charge carrier transfer is favorable in trimer- and polymer-encapsulated SWNTs because they are type-II heterojunctions. On the other hand, we have employed the time-domain nonadiabatic dynamics simulation approach to explore the interfacial carrier dynamics in type-II polymer-encapsulated SWNT heterojunctions. It is found that the electron and hole transfer processes are asymmetric and occur in opposite directions and at different rates. The former takes place from polymers to SWNTs in an ultrafast way (ca. 370 fs), whereas the latter occurs slowly from SWNTs to polymers (ca. 24 ps). A closer analysis uncovers the fact that the different carrier transfer rates mainly originate from the different densities of the acceptor states, energy differences and inter-state couplings between the donor and acceptor states. Finally, the present work demonstrates that the polymerization degree could act as a new regulating strategy to tune the interfacial properties of molecule-encapsulated SWNT heterojunctions.

The spin-orbit interaction controls photoinduced interfacial electron transfer in fullerene-perovskite heterojunctions: C60versus C70.

Here, we used collinear and noncollinear density functional theory (DFT) methods to explore the interfacial properties of two heterojunctions between a fullerene (C60 and C70) and the MAPbI3(110) surface. Methodologically, consideration of the spin-orbit interaction has been proven to be required to obtain accurate energy-level alignment and interfacial carrier dynamics between fullerenes and perovskites in hybrid perovskite solar cells including heavy atoms (such as Pb atoms). Both heterojunctions are predicted to be the same type-II heterojunction, but the interfacial electron transfer process from MAPbI3 to C60 is completely distinct from that to C70. In the former, the interfacial electron transfer is slow because of the associated large energy gap, and the excited electrons are thus trapped in MAPbI3 for a while. In contrast, in the latter, the smaller energy gap induces ultrafast electron transfer from MAPbI3 to C70. These points are further supported by DFT-based nonadiabatic dynamics simulations including the spin-orbit coupling (SOC) effects. These gained insights could help rationally design superior fullerene-perovskite interfaces to achieve high power conversion efficiencies of fullerene-perovskite solar cells.

Simulation of UV absorption spectra and relaxation dynamics of uracil and uracil-water clusters.

Despite many studies, the mechanisms of nonradiative relaxation of uracil in the gas phase and in aqueous solution are still not fully resolved. Here we combine theoretical UV absorption spectroscopy with nonadiabatic dynamics simulations to identify the photophysical mechanisms that can give rise to experimentally observed decay time constants. We first compute and theoretically assign the electronic spectra of uracil using the second-order algebraic-diagrammatic-construction (ADC(2)) method. The obtained electronic states, their energy differences and state-specific solvation effects are the prerequisites for understanding the photodynamics. We then use nonadiabatic trajectory-surface-hopping dynamics simulations to investigate the photoinduced dynamics of uracil and uracil-water clusters. In contrast to previous studies, we found that a single mechanism - the ethylenic twist around the C[double bond, length as m-dash]C bond - is responsible for the ultrafast component of the nonradiative decay, both in the gas phase and in solution. Very good agreement with the experimentally determined ultrashort decay time constants is obtained.

Excimer formation dynamics in the isolated tetracene dimer.

The understanding of excimer formation and its interplay with the singlet-correlated triplet pair state 1(TT) is of high significance for the development of efficient organic electronics. Here, we study the photoinduced dynamics of the tetracene dimer in the gas phase by time-resolved photoionisation and photoion imaging experiments as well as nonadiabatic dynamics simulations in order to obtain mechanistic insight into the excimer formation dynamics. The experiments are performed using a picosecond laser system for excitation into the S2 state and reveal a biexponential time dependence. The time constants, obtained as a function of excess energy, lie in the range between ≈10 ps and 100 ps and are assigned to the relaxation of the excimer on the S1 surface and to its deactivation to the ground state. Simulations of the quantum-classical photodynamics are carried out in the frame of the semi-empirical CISD and TD-lc-DFTB methods. Both theoretical approaches reveal a dominating relaxation pathway that is characterised by the formation of a perfectly stacked excimer. TD-lc-DFTB simulations have also uncovered a second relaxation channel into a less stable dimer conformation in the S1 state. Both methods have consistently shown that the electronic and geometric relaxation to the excimer state is completed in less than 10 ps. The inclusion of doubly excited states in the CISD dynamics and their diabatisation further allowed to observe a transient population of the 1(TT) state, which, however, gets depopulated on a timescale of 8 ps, leading finally to the trapping in the excimer minimum.