Ultrafast Photoinduced Dynamics Research Articles

Conformational and Solvent Effects on the Photoinduced Electron Transfer Dynamics of a Zinc Phthalocyanine-Benzoperylenetriimide Conjugate: A Nonadiabatic Dynamics Simulation.

Herein, we employed a combination of static electronic structure calculations and nonadiabatic dynamics simulations at linear-response time dependent density functional theory (LR-TDDFT) level with the optimally tuned range-separated hybrid (OT-RSH) functional to explore the ultrafast photoinduced dynamics of a zinc phthalocyanine-benzoperylenetriimide (ZnPc-BPTI) conjugate. Due to the flexibility of the linker, we identified two major conformations: the stacked conformation (ZnPc-BPTI-1) and the extended conformation (ZnPc-BPTI-2). Since the charge transfer states are much lower than the lowest local excitation in ZnPc-BPTI-1, which is contrary to ZnPc-BPTI-2, the ultrafast electron transfer (~3.6 ps) is only observed in the nonadiabatic simulations of ZnPc-BPTI-1 upon local excitation around the absorption maximum of ZnPc. However, when considering the solvent effects in benzonitrile: the lowest S1 states are both charge transfer states from ZnPc to BPTI for different conformers. Subsequent nonadiabatic dynamics simulations indicate that both conformers experience ultrafast electron transfer in benzonitrile with two time constants of 90 [100] fs and 1.40 [1.43] ps. Our present work not only agrees well with previous experimental study, but also points out the important role of conformational changes and solvent effects in regulating the photodynamics of organic donor-acceptor conjugates.

Photoinduced Nonadiabatic Dynamics of a Single-Walled Carbon Nanotube-Porphyrin Complex.

Single-walled carbon nanotubes (SWCNTs) have gained a lot of attention in the past few decades due to their promising optoelectronic properties. In addition, SWCNTs can form complexes that have good chemical stability and transport properties with other optical functional materials through noncovalent interactions. Elucidating the detailed mechanism of these complexes is of great significance for improving their optoelectronic properties. Nevertheless, simulating the photoinduced dynamics of these complexes accurately is rather challenging since they usually contain hundreds of atoms. To save computational efforts, most of the previous works have ignored the excitonic effects by employing nonadiabatic carrier (electron and hole) dynamics simulations. To properly consider the influence of excitonic effects on the photoinduced ultrafast processes of the SWCNT-tetraphenyl porphyrin (H2TPP) complex and to further improve the computational efficiency, we developed the nonadiabatic molecular dynamics (NAMD) method based on the extended tight binding-based simplified Tamm-Dancoff approximation (sTDA-xTB), which is applied to study the ultrafast photoinduced dynamics of the noncovalent SWCNT-porphyrin complex. In combination with statically electronic structure calculations, the present work successfully reveals the detailed microscopic mechanism of the ultrafast excitation energy transfer process of the complex. Upon local excitation on the H2TPP molecule, an ultrafast energy transfer process occurs from H2TPP (SWCNT-H2TPP*) to SWCNT (SWCNT*-H2TPP) within 10 fs. Then, two slower processes corresponding to the energy transfer from H2TPP to SWCNT and hole transfer from H2TPP to SWCNT take place in the 1 ps time scale. The sTDA-xTB-based electronic structure calculation and NAMD simulation results not only match the previous experimental observations from static and transient spectra but also provide more insights into the detailed information on the complex's photoinduced dynamics. Therefore, the sTDA-xTB-based NAMD method is a powerful theoretical tool for studying the ultrafast photoinduced dynamics in large extended systems with a large number of electronically excited states, which could be helpful for the subsequent design of SWCNT-based functional materials.

Simultaneous tracking of ultrafast surface and gas-phase dynamics in solid-gas interfacial reactions.

Real-time detection of intermediate species and final products at the surface and near-surface in interfacial solid-gas reactions is critical for an accurate understanding of heterogeneous reaction mechanisms. In this article, an experimental method that can simultaneously monitor the ultrafast dynamics at the surface and above the surface in photoinduced heterogeneous reactions is presented. This method relies on a combination of mass spectrometry and femtosecond pump-probe spectroscopy. As a model system, the photoinduced reaction of methyl iodide on and above a cerium oxide surface is investigated. The species that are simultaneously detected from the surface and gas-phase present distinct features in the mass spectra, such as a sharp peak followed by an adjacent broad shoulder. The sharp peak is attributed to the species detected from the surface, while the broad shoulder is due to the detection of gas-phase species above the surface, as confirmed by multiple experiments. By monitoring the evolution of the sharp peak and broad shoulder as a function of the pump-probe time delay, transient signals are obtained that describe the ultrafast photoinduced reaction dynamics of methyl iodide on the surface and in the gas-phase. Finally, SimION simulations are performed to confirm the origin of the ions produced on the surface and in the gas-phase.

Ultrafast Photoinduced Dynamics of Styryl-Substituted BODIPY Dyes and Their Aggregates

Ultrafast Photoinduced Dynamics of Styryl-Substituted BODIPY Dyes and Their Aggregates

Ultrafast Photoinduced Dynamics in 1,3-Cyclohexadiene: A Comparison of Trajectory Surface Hopping Schemes†.

Photoinduced nonadiabatic processes play a crucial role in a wide range of disciplines, from fundamental steps in biology to modern applications in advanced materials science. A theoretical understanding of these processes is highly desirable, and trajectory surface hopping (TSH) has proven to be a well-suited framework for a wide range of systems. In this work, we present a comprehensive comparison between two TSH algorithms, the conventional Tully's fewest switches surface hopping (FSSH) scheme and the Landau-Zener surface hopping (LZSH), to study the photoinduced ring-opening of 1,3-cyclohexadiene (CHD) to 1,3,5-hexatriene at the spin-flip time-dependent density functional theory (SF-TDDFT) level of theory. Additionally, we compare our results with a literature study at the extended multistate complete active space second-order perturbation theory method (XMS-CASPT2) level of theory. Our results show that the average population and lifetimes estimated with LZSH using SF-TDDFT are closer to the literature (using multireference methods) than those estimated with FSSH using SF-TDDFT. The latter speaks in favor of applying LZSH in combination with the SF-TDDFT method to study larger and more complex systems such as molecular photoswitches where the CHD molecule acts as a backbone. In addition, we present an implementation of Tully's FSSH algorithm as an extension to the PySurf software package.

Understanding the Photoinduced Desorption and Oxidation of CO on Ru(0001) Using a Neural Network Potential Energy Surface.

The study of ultrafast photoinduced dynamics of adsorbates on metal surfaces requires thorough investigation of laser-excited electrons and, in many cases, the highly excited surface lattice. While ab initio molecular dynamics with electronic friction and thermostats (Te, Tl)-AIMDEF addresses such complex modeling, it imposes severe computational costs, hindering quantitative comparison with experimental desorption probabilities. In order to bypass this limitation, we utilize the embedded atom neural network method to construct a potential energy surface (PES) for the coadsorption of CO and O on Ru(0001). Our results demonstrate that this PES not only reproduces the short-time ab initio dynamics but is also able to yield statistically significant data for long lasting trajectories that correlate well with experimental findings. Furthermore, the analysis of the laser-induced dynamics reveals the existence of a dynamic trapping state that acts as a precursor for CO desorption, and it is not observed under thermal conditions. Altogether, our results validate the underlying theoretical framework, providing robust support for the description of not only the photoinduced desorption but also the oxidation of CO in terms of nonequilibrated but thermal hot electrons and phonons.

Ultrafast photo-induced carrier dynamics of perovskite quantum dots during structural degradation.

In this study, the ultrafast photo-induced carrier dynamics of red-emitting PQDs during structural degradation was investigated using time-resolved transient absorption spectroscopy. The spectroscopic analysis revealed how the carrier dynamics varied when PQDs were exposed to a polar solvent. Three decay modes (carrier trapping, radiative carrier recombination and trap-assisted non-radiative recombination) were proposed to analyze the carrier dynamics of PQDs. The light-emitting property of PQDs is primarily influenced by radiative carrier recombination. This study demonstrates that structural degradation induced halide migration within PQDs and the formation of defects within the crystal lattice, leading to a proliferation of carrier trapping states. The increased trap states led to a reduction in carriers undergoing radiative carrier recombination. Additionally, PQDs degradation accelerated radiative carrier recombination, indicating a faster escape of carriers from excited states. Consequently, these factors hinder carriers remaining in excited states, leading to a decline in the light-emitting property of PQDs. Nevertheless, increasing an excitation fluence could reduce the carrier trapping mode and increase the radiative carrier recombination mode, suggesting a diminishment of the impact of carrier trapping. These findings offer a more comprehensive understanding of structural degradation of PQDs and can contribute to the development of PQDs with high structural stability.

Appearance of a Photoinduced Hidden State in the Electron Donor–Acceptor Type Metal–Organic Framework (NPr4)2[Fe2(Cl2An)3

AbstractElectron donor–acceptor (DA)‐type metal–organic frameworks (MOFs) with valence instability are promising molecular materials for the design of photo‐responsive and electronic/magnetic functional materials. Here, ultrafast photoinduced dynamics in a DA‐type layered MOF that exhibits a charge‐transfer (CT)‐type phase transition are reported: (NPr4)2[Fe2(Cl2An)3], where NPr4+ = tetra‐n‐propylammonium and Cl2An2− = 2,5‐dichloro‐3,6‐dihydroxo‐1,4‐benzoquinonate. At room temperature (300 K: RT), ultrafast photoinduced CT between the Fe and Cl2An ions induces a sensitive change in the state associated with the valence instability from a single‐chain, electron‐correlated state to a new photoinduced, structurally modulated state. In the photoinduced state, two absorption bands are observed, one on the higher‐energy side of the CT band and the other in the mid‐IR range. This strongly implies that the local inversion center on the Cl2An ion that exists in the initial state disappears instantly upon photoexcitation, causing an ultrafast change in the lattice structure due to the softening of rigid bonds. This has never been realized in thermal excitation. These findings demonstrate that a new electronic state with a unique lattice structure—i.e., a photoinduced hidden state—appears in this MOF system at ultra‐high speed (within 110 fs) upon photoexcitation at RT.

Tuning UV Pump X-ray Probe Spectroscopy on the Nitrogen K Edge Reveals the Radiationless Relaxation of Pyrazine: Ab Initio Simulations Using the Quasiclassical Doorway-Window Approximation.

Transient absorption UV pump X-ray probe spectroscopy has been established as a versatile technique for the exploration of ultrafast photoinduced dynamics in valence-excited states. In this work, an ab initio theoretical framework for the simulation of time-resolved UV pump X-ray probe spectra is presented. The method is based on the description of the radiation-matter interaction in the classical doorway-window approximation and a surface-hopping algorithm for the nonadiabatic nuclear excited-state dynamics. Using the second-order algebraic-diagrammatic construction scheme for excited states, UV pump X-ray probe signals were simulated for the carbon and nitrogen K edges of pyrazine, assuming a duration of 5 fs of the UV pump and X-ray probe pulses. It is predicted that spectra measured at the nitrogen K edge carry much richer information about the ultrafast nonadiabatic dynamics in the valence-excited states of pyrazine than those measured at the carbon K edge.

Ultrafast Photoinduced Dynamics of Quaterthiophene-Squaraine Hybrid Aggregates

Photoinduced energy transfer, charge transfer, and generation of sufficiently long-lived charge-separated (CS) states in the aggregated oligothiophenes are always challenging. Herein, we have coupled quaterthiophene (QTH) with a squaraine (SQR) dye in hybrid aggregates. A detailed time-resolved investigation using transient absorption spectroscopy and global target analyses revealed ultrafast photoinduced energy and electron transfer from QTH aggregates to SQR aggregates and the formation of a long-lived CS state in these hybrids. The pulse width limited energy transfer (<120 fs) occurred from the S1(Agg.)Ex. state, and the electron transfer occurred from both the S1(Agg.)Ex. state and the S1(Agg.)Rlx. state of QTH aggregates to the SQR aggregates at the timescales 131.5 ps and 3.3 ns, respectively. The resulting CS state lived for more than 8 ns. Moreover, the electrons of the QTH aggregates were prohibited to relax via the dark state and were extracted to the SQR aggregates which would lead to their successful utilization toward light-harvesting applications.

Femtosecond imaging of giant-hemeprotein with XFEL pulses

Outrunning radiation damage, extremely intense femtosecond pulses of x-ray free-electron lasers (XFELs) open up the possibility of imaging the structure and dynamics of macromolecules frozen in time at room temperature. Single-Particle Imaging (SPI) of uncrystallized macromolecules at high-resolution is one of the most-desired foundational applications of XFELs and one of the ultimate goals of SPI is to image the light-induced ultrafast (ps/fs) dynamics in single-macromolecules. Biological proteins exhibiting photoinduced ultrafast dynamics are in the range of tens to few-hundreds of kDa, which are too small for SPI with the photon flux of current generation XFELs. Ideally, one needs MDa-sized, strongly scattering, photoactive proteins for such challenging endeavours to discern the signal above the background scattering and to obtain difference-maps with sufficient quality to elucidate photoinduced changes empirically. Photoactive proteins are sparse in nature and MDa-sized photoactive macromolecules are extremely rare. We have found one such rare MDa-sized photoactive, porphyrin-containing, large-metalloprotein-complex, the giant-hemeprotein—erythrocruorin (Ery) and show that Ery is likely suitable for validating the ultimate potential of SPI. We present the cryoEM characterization of stability of Ery in the unique experimental conditions of XFEL-SPI together with simulated single-molecule diffraction and 3D intensity reconstruction using expand-maximize-compress (EMC) algorithm and propose a potential SPI roadmap to demonstrate the imaging of ps/fs resolved bio-functional dynamics in Ery with XFEL pulses. Also, here we report the first in-solution ensemble fluctuation scattering results of Ery with the microfocus hard x-ray FEL pulses at the Linac Coherent Light Source (LCLS), USA—a step towards single-molecule imaging of Ery in-solution with nanofocus. We envisage that the robust giant-hemeprotein Ery could likely be an archetype biological macromolecular system enabling the imaging of light-induced ultrafast (ps/fs) dynamics such as protein-quake following heme-doming in isolated single-proteins—“the Holy Grail” of XFEL-SPI.

Ultrafast photoinduced carrier dynamics in single crystalline perovskite films

Carrier dynamic processes in CsPbBr3 single crystalline perovskite, including hot carrier cooling, defect state trapping and carrier recombination, were studied using micro-region transient absorption technique.

Ultrafast photoinduced dynamics of a donor-(mathrm pi)bridge-acceptor based merocyanine dye

Merocyanine dyes are of great interest amongst researchers due to their nonlinear optical (NLO) properties and solvatochromism. Molecular structure of these dyes constitutes conjugated pathway between the donor and acceptor substituents, with lowest energy transition of mathrm pi–mathrm pi* character. To rationalize the design of these dyes and deduce structure-property relationship, it is eminent to unravel the excited state dynamics in these complex molecular structures in different solvents. Here we have studied excited state dynamics of a merocyanine dye known as HB194, which has shown commendable efficiency in small molecule based bulk heterojuction solar cells. We have employed femtosecond transient absorption in combination with the quantum chemistry calculations to unravel the solvent dependent charge transfer dynamics of HB194. The excited state decays of the HB194 in different solvents show multi-exponential components. The analysis of the time-resolved data reveals that the polar solvents induce conformationally relaxed intramolecular charge transfer state. In non-polar solvent cyclohexane, only solvent-stabilized ICT state is observed. Additionally, we observe an anomalously red-shifted emission in ethylene glycol centred at sim 750 nm. Our computational calculations suggest the presence of molecular dimers resulting into observed red-shifted emission band. Our work therefore underscores the importance of gathering molecular-level insight into the system-bath interactions for designing next generation merocynanine-based solvatochromic dyes.

Ultrafast photo-induced dynamics of $$\hbox {V}_{2} \hbox {O}_{3}$$ thin films under hydrostatic pressure

Controlling material properties with light pulses represents one of the next great challenge in material science. To achieve this goal, one needs to impact the material on the relevant time scale for controlling electronic and phononic properties. Targeting this challenge becomes possible thanks to the emerging field of photo-induced phase transition when a femtosecond light pulse interacts with the system. Along this line, we demonstrate the possibility to perform femtosecond optical spectroscopy under control thermodynamical environment. This new experimental setup includes a very precise pressure control between 1 and 6 kbar. These experimental results clearly demonstrate an effect of hydrostatic pressure onto the out-of-equilibrium photo-response of \(\hbox {V}_{2} \hbox {O}_{3}\). The main feature is a blue shift of the Brillouin frequency that correlates with an increasing speed of sound.

Second-Order Photoinduced Reflectivity for Retrieval of the Dynamics in Plasmonic Nanostructures.

Measuring the change in reflectivity (ΔR) using the traditional pump–probe approach can monitor photoinduced ultrafast dynamics in matter, yet relating these dynamic to physical processes for complex systems is not unique. By applying a simple modification to the classical pump–probe technique, we simultaneously measure both the first and second order of ΔR. These additional data impose new constraints on the interpretation of the underlying ultrafast dynamics. In the first application of the approach, we probe the dynamics induced by a pump laser on the local-surface plasmon resonance (LSPR) in gold nanoantennas. Measurements of ΔR over several picoseconds and a wide range of probe wavelengths around the LSPR peak are followed by data fitting using the two-temperature model. The constraints, imposed by the second-order data, lead us to modify the model and force us to include the contribution of nonthermalized electrons in the early stages of the dynamics.

Ultrafast photo-induced processes in complex environments: The role of accuracy in excited-state energy potentials and initial conditions

Light induces non-equilibrium time evolving molecular phenomena. The computational modeling of photo-induced processes in large systems, embedded in complex environments (i.e., solutions, proteins, materials), demands for a quantum and statistical mechanic treatment to achieve the required accuracy in the description of both the excited-state energy potentials and the choice of the initial conditions for dynamical simulations. On the other hand, the theoretical investigation on the atomistic scale of times and sizes of the ultrafast photo-induced reactivity and non-equilibrium relaxation dynamics right upon excitation requests tailored computational protocols. These methods often exploit hierarchic computation schemes, where a large part of the degrees of freedom are required to be treated explicitly to achieve the right accuracy. Additionally, part of the explicit system needs to be treated at ab initio level, where density functional theory, using hybrid functionals, represents a good compromise between accuracy and computational cost, when proton transfers, non-covalent interactions, and hydrogen bond dynamics play important roles. Thus, the modeling strategies presented in this review stress the importance of hierarchical quantum/molecular mechanics with effective non-periodic boundary conditions and efficient phase-sampling schemes to achieve chemical accuracy in ultrafast time-resolved spectroscopy and photo-induced phenomena. These approaches can allow explicit and accurate treatment of molecule/environment interactions, including also the electrostatic and dispersion forces of the bulk. At the same time, the specificities of the different case studies of photo-induced phenomena in solutions and biological environments are highlighted and discussed, with special attention to the computational and modeling challenges.

Ultrafast light-induced THz switching in exchange-biased Fe/Pt spintronic heterostructure

The ultrafast optical control of magnetization in spintronic structures enables one to access to the high-speed information processing, approaching the realm of terahertz (THz). Femtosecond visible/near-infrared laser-driven ferromagnetic/nonmagnetic metallic spintronic heterostructures-based THz emitters combine the aspects from the ultrafast photo-induced dynamics and spin-charge inter-conversion mechanisms through the generation of THz electromagnetic pulses. In this Letter, we demonstrate photoexcitation density-dependent induced exchange-bias tunability and THz switching in an annealed Fe/Pt thin-film heterostructure, which otherwise is a widely used conventional spintronic THz emitter. By combining the exchange-bias effect along with THz emission, the photo-induced THz switching is observed without any applied magnetic field. These results pave the way for an all-optical ultrafast mechanism to exchange-bias tuning in spintronic devices for high-density storage, read/write magnetic memory applications.

Imaging nanostructure phase transition through ultrafast far-field optical ultramicroscopy

Imaging photo-induced ultrafast dynamics of nanostructure phase transition is of great interest to the fields of laser-matter interactions and nanotechnology. However, conventional ultrafast far-field optical imaging methods cannot image nanostructures as their scattering scales as D 6 , with D being the diamater, leading to a vanishing signal-to-noise ratio. Here, we use ultrafast ultramicroscopy to capture the spatiotemporal evolution of surface nanostructures as they undergo melting, spallation, and re-solidification processes. Our experimental observations, combined with finite difference time domain (FDTD) simulations, show agreement with molecular dynamic simulations on ultrashort laser pulse-irradiated metallic nanoparticles and suggest the occurrence of melting of nanostructures followed by photomechanical spallation within a few picoseconds. At longer timescales, we image the re-solidification dynamics of the melted nanostructures occurring within nanoseconds. The re-solidification time for nanostructured surface occurs an order of magnitude faster than for an initially flat surface. Our study demonstrates a simple but powerful far-field optical approach for studying ultrafast dynamics of nanostructures. • Introducing an optical far-field ultrafast imaging method for nanostructures • Imaging photomechanical spallation of nanostructures within picoseconds • Imaging the re-solidification dynamics of nanostructures Ultrafast imaging of nanostructures is challenging due to their low signal-to-noise-ratio. ElKabbash et al. use ultrafast ultramicroscopy to image light-matter interactions at the nanoscale, spatial, and femtosecond scale temporally. The results show that irradiating surface nanostructures with an intense femtosecond laser pulse undergo photomechanical spallation within a few picoseconds.

Ultrafast photo-induced carrier dynamics of FAPbI3-MAPbBr3 perovskite films fabricated with additives and a hole transport material

In this study, mixed perovskite films of formamidinium lead triiodide (HC(NH2)2PbI3, FAPbI3) and methylammonium lead tribromide (CH3NH3PbBr3, MAPbBr3) were fabricated differently with solution additive methods and a presence of a hole transport material (HTM). We utilized ultrafast time-resolved transient absorption spectroscopy (TAS) in order to investigate the carrier generation and decay dynamics. The photo-induced carrier dynamics changes according to additive methods and applying the HTM. The HTM affects dominantly a TA decay constant of long-time scale. On the other hand, additive methods reduce a time constant of short-time scale and also increase the density of the photo-induced carrier.

String-Attached Oligothiophene Substituents Determine the Fate of Excited States in Ruthenium Complexes for Photodynamic Therapy.

We explore the photophysical properties of a family of Ru(II) complexes, Ru-ip-nT, designed as photosensitizers (PSs) for photodynamic therapy (PDT). The complexes incorporate a 1H-imidazo[4,5-f][1,10]-phenanthroline (ip) ligand appended to one or more thiophene rings. One of the complexes studied herein, Ru-ip-3T (known as TLD1433), is currently in phase II human clinical trials for treating bladder cancer by PDT. The potent photocytotoxicity of Ru-ip-3T is attributed to a long-lived intraligand charge-transfer triplet state. The accessibility of this state changes upon varying the length (n) of the oligothiophene substituent. In this paper, we highlight the impact of n on the ultrafast photoinduced dynamics in Ru-ip-nT, leading to the formation of the function-determining long-lived state. Femtosecond time-resolved transient absorption combined with resonance Raman data was used to map the excited-state relaxation processes from the Franck-Condon point of absorption to the formation of the lowest-energy triplet excited state, which is a triplet metal-to-ligand charge-transfer excited state for Ru-ip-0T-1T and an oligothienyl-localized triplet intraligand charge-transfer excited state for Ru-ip-2T-4T. We establish the structure-activity relationships with regard to changes in the excited-state dynamics as a function of thiophene chain length, which alters the photophysics of the complexes and presumably impacts the photocytotoxicity of these PSs.