Photoinduced Charge Transfer Dynamics Research Articles

Instantaneous Marcus theory for photoinduced charge transfer dynamics in multistate harmonic model systems

Modeling the dynamics of photoinduced charge transfer (CT) in condensed phases presents challenges due to complicated many-body interactions and the quantum nature of electronic transitions. While traditional Marcus theory is a robust method for calculating CT rate constants between electronic states, it cannot account for the nonequilibrium effects arising from the initial nuclear state preparation. In this study, we employ the instantaneous Marcus theory (IMT) to simulate photoinduced CT dynamics. IMT incorporates nonequilibrium structural relaxation following a vertical photoexcitation from the equilibrated ground state, yielding a time-dependent rate coefficient. The multistate harmonic (MSH) model Hamiltonian characterizes an organic photovoltaic carotenoid-porphyrin-fullerene triad dissolved in explicit tetrahydrofuran solvent, constructed by mapping all-atom inputs from molecular dynamics simulations. Our calculations reveal that the electronic population dynamics of the MSH models obtained with IMT agree with the more accurate quantum-mechanical nonequilibrium Fermi’s golden rule. This alignment suggests that IMT provides a practical approach to understanding nonadiabatic CT dynamics in condensed-phase systems.

Semiclassical approaches to perturbative time-convolution and time-convolutionless quantum master equations for electronic transitions in multistate systems.

Understanding the dynamics of photoinduced processes in complex systems is crucial for the development of advanced energy-conversion materials. In this study, we investigate the nonadiabatic dynamics using time-convolution (TC) and time-convolutionless (TCL) quantum master equations (QMEs) based on treating electronic couplings as perturbation within the framework of multistate harmonic (MSH) models. The MSH model Hamiltonians are mapped from all-atom simulations such that all pairwise reorganization energies are consistently incorporated, leading to a heterogeneous environment that couples to the multiple electronic states differently. Our exploration encompasses the photoinduced charge transfer dynamics in organic photovoltaic carotenoid-porphyrin-C60 triad dissolved in liquid solution and the excitation energy transfer (EET) dynamics in photosynthetic Fenna-Matthews-Olson complexes. By systematically comparing the perturbative TC and TCL QME approaches with exact quantum-mechanical and various semiclassical approximate kernels, we demonstrate their efficacy and accuracy in capturing the essential features of photoinduced dynamics. Our calculations show that TC QMEs generally yield more accurate results than TCL QMEs, especially in EET, although both methods offer versatile approaches adaptable across different systems. In addition, we investigate various semiclassical approximations featuring the Wigner-transformed and classical nuclear densities as well as the governing dynamics during the quantum coherence period, highlighting the trade-off between accuracy and computational cost. This work provides valuable insights into the applicability and performance of TC and TCL QME approaches via the MSH model, offering guidance for realistic applications to condensed-phase systems on the atomistic level.

All-Atom Photoinduced Charge Transfer Dynamics in Condensed Phase via Multistate Nonlinear-Response Instantaneous Marcus Theory.

Photoinduced charge transfer (CT) in the condensed phase is an essential component in solar energy conversion, but it is challenging to simulate such a process on the all-atom level. The traditional Marcus theory has been utilized for obtaining CT rate constants between pairs of electronic states but cannot account for the nonequilibrium effects due to the initial nuclear preparation. The recently proposed instantaneous Marcus theory (IMT) and its nonlinear-response formulation allow for incorporating the nonequilibrium nuclear relaxation to electronic transition between two states after the photoexcitation from the equilibrium ground state and provide the time-dependent rate coefficient. In this work, we extend the nonlinear-response IMT method for treating photoinduced CT among general multiple electronic states and demonstrate it in the organic photovoltaic carotenoid-porphyrin-fullerene triad dissolved in explicit tetrahydrofuran solvent. All-atom molecular dynamics simulations were employed to obtain the time correlation functions of energy gaps, which were used to generate the IMT-required time-dependent averages and variances of the relevant energy gaps. Our calculations show that the multistate IMT could capture the significant nonequilibrium effects due to the initial nuclear state preparation, and this is corroborated by the substantial differences between the population dynamics predicted by the multistate IMT and the Marcus theory, where the Marcus theory underestimates the population transfer. The population dynamics by multistate IMT is also shown to have a better agreement with the all-atom nonadiabatic mapping dynamics than the Marcus theory does. Because the multistate nonlinear-response IMT is straightforward and cost-effective in implementation and accounts for the nonequilibrium nuclear effects, we believe this method offers a practical strategy for studying charge transfer dynamics in complex condensed-phase systems.

Generalized nonequilibrium Fermi's golden rule and its semiclassical approximations for electronic transitions between multiple states.

The nonequilibrium Fermi's golden rule (NE-FGR) approach is developed to simulate the electronic transitions between multiple excited states in complex condensed-phase systems described by the recently proposed multi-state harmonic (MSH) model Hamiltonian. The MSH models were constructed to faithfully capture the photoinduced charge transfer dynamics in a prototypical organic photovoltaic carotenoid-porphyrin-C60 molecular triad dissolved in tetrahydrofuran. A general expression of the fully quantum-mechanical NE-FGR rate coefficients for transitions between all pairs of states in the MSH model is obtained. Besides, the linearized semiclassical NE-FGR formula and a series of semiclassical approximations featuring Wigner and classical nuclear sampling choices and different dynamics during the quantum coherence period for the MSH model are derived. The current approach enables all the possible population transfer pathways between the excited states of the triad, in contrast to the previous applications that only addressed the donor-to-acceptor transition. Our simulations for two triad conformations serve as a demonstration for benchmarking different NE-FGR approximations and show that the difference between all levels of approximation is small for the current system, especially at room temperature. By comparing with nonadiabatic semiclassical dynamics, we observe similar timescales for the electronic population transfer predicted by NE-FGR. It is believed that the general formulation of NE-FGR for the MSH Hamiltonian enables a variety of applications in realistic systems.

Solvent-Induced Symmetry Breaking of the Photoinduced Charge Transfer Dynamics in the Bridged Perylene Dimer

Solvent-Induced Symmetry Breaking of the Photoinduced Charge Transfer Dynamics in the Bridged Perylene Dimer

Facet-engineered photo-induced charge transfer dynamics at the interface of cubic CsPbBr3 and organic acceptor molecules

Perovskite, particularly halide perovskite shows tremendous application in the field of optoelectronic devices such as Light emitting diode (LED) and solar cells. Semiconducting nanomaterials like perovskite nanomaterials have photoactive components and are used as electron as well as hole donors. A hybrid combination of organic acceptors such as Anthraquinone (AQ) and Tetracyanoquinodimethane (TCNQ) with CsPbX3 (X = Cl, Br, I) perovskite nanomaterials at the interface is a unique path for charge separation. The surface of the perovskite nanomaterial plays an important role in the electron-hole charge separation. The surface of the perovskite nanomaterial is responsible for the interaction between this redox couple. Only those molecules show better charge separation which interacts more efficiently with the excited state of the perovskite nanocrystals (PNCs), but very few organic molecules show this kind of redox properties. In the present study, we employed AQ and TCNQ to extract charges from PNCs. We performed photoluminescence (PL) and time-correlated single photon count spectroscopy (TCSPC) to investigate the impacts of both organic acceptor molecules on the lifetime and photoluminescence (PL) of PNCs. PNCs possessed distinct lifetime and luminous characteristics prior to and after the incorporation of quenchers, however, in the case of TCNQ, improved charge separation occurred, as evidenced by PL and TCSPC. We additionally employed SEM (scanning electron microscopy) and TEM (transmission electron microscopy) to investigate the influence of the quencher on morphology.

Greatly Enhanced Raman Scattering of Graphene on Metals by a Boron Nitride Film Covering.

Raman spectroscopy, a nondestructive fingerprinting technique, is mainly utilized to identify molecular species and phonon modes of materials. However, direct Raman characterization of two-dimensional materials typically synthesized on catalytic metal substrates is extremely challenging because of the significant electric screening and interfacial electronic couplings. Here, we demonstrate that by covering as-grown graphene with boron nitride (BN) films, the Raman intensity of graphene can be enhanced by two orders of magnitude and is also several times stronger than that of suspended graphene. This great Raman enhancement originates from the optical field amplification by Fabry-Pérot cavity in BN films and the local field plasmon near copper steps. We further demonstrate the direct characterization of the local strain and doping level of as-grown graphene and in situ monitoring of the molecule reaction process by enhanced Raman spectroscopy. Our results will broaden the optical investigations of interfacial sciences on metals, including photoinduced charge transfer dynamics and photocatalysis at metal surfaces.

Exploring the Role of Short Chain Acids as Surface Ligands in Photoinduced Charge Transfer Dynamics from CsPbBr3 Perovskite Nanocrystals

The most commonly used surface capping ligands, like oleic acid and oleylamine, passivate the surface of perovskite nanocrystals (PNCs) to enhance their stability and optical properties. However, due to their inherent insulating nature, charge transport across the surface of the PNCs is hindered, limiting their application in devices. In this study, we have post-treatment CsPbBr3 PNCs with short chain ligands benzoic acid (BA) and ascorbic acid (AA) and observed that both acid-treated PNCs show enhanced stability and optical properties. Still, BA-treated PNCs show the highest charge transport rate due to their conjugating nature. The photoelectrochemical measurements also show the most efficient electron flow across the surface of the PNC with BA-treated PNCs. A longer carrier lifetime and fast charge transfer make BA-treated PNCs ideal candidates for application in real-life devices.

Mechanistic insights into photoinduced energy and charge transfer dynamics between magnesium-centered tetrapyrroles and carbon nanotubes.

Functionalizing single-walled carbon nanotubes (SWNTs) with light-harvesting molecules is a facile way to construct donor-acceptor nanoarchitectures with intriguing optoelectronic properties. Magnesium-centered bacteriochlorin (MgBC), chlorin (MgC), and porphyrin (MgP) are a series of tetrapyrrole macrocycles comprising a central metal and four coordinated aromatic or antiaromatic five-membered rings linked by methine units, which show excellent visible light absorption. To delineate the effects of the aromaticity of coordinated rings on the optoelectronic properties of the nanocomposites, the photoinduced energy and charge transfer dynamics between Mg-centered tetrapyrroles and SWNTs are explored. The results show that excited energy transfer (EET) can occur within MgP@SWNT ascribed to the stabilization of the highest occupied molecular orbital (HOMO) in MgP with the increase of aromatic coordinated rings, while only electron transfer can take place in MgBC@SWNT and MgC@SWNT. Non-adiabatic dynamics simulations demonstrate that electron and hole transfer from MgP to SWNT is asynchronous. The electron transfer is ultrafast with a timescale of ca. 50 fs. By contrast, the hole transfer is significantly suppressed, although it can be accelerated to some extent when using a lower excitation energy of 2.2 eV as opposed to 3.1 eV. Further analysis reveals that the large energy gaps between charge-donor and charge-acceptor states play a crucial role in regulating photoexcited state relaxation dynamics. Our theoretical insights elucidate the structure-functionality interrelations between Mg-centered tetrapyrroles and SWNTs and provide a comprehensive understanding of the underlying charge transfer mechanism within MgP@SWNT nanocomposites, which paves the way for the forthcoming development of SWNT-based photo-related functional materials with targeted applications.

Photon-Energy-Dependent Reversible Charge Transfer Dynamics of Double Perovskite Nanocrystal-Polymer Nanocomposites.

Combining steady-state photoluminescence and transient absorption (TA) spectroscopy, we have investigated the photoinduced charge transfer dynamics between lead-free Mn-doped Cs2NaIn0.75Bi0.25Cl6 double perovskite (DP) nanocrystals (NCs) and conjugated poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylenevinylene] (MDMO-PPV). Upon ultraviolet-A excitation, the photoinduced absorption feature of DP NCs/MDMO-PPV nanocomposites disappeared, and the stimulated emission weakened in the TA spectrum. This was due to charge transfer from the MDMO-PPV polymers to DP NCs. Upon a higher photon-energy ultraviolet-C excitation, stimulated emission and photoinduced absorption features vanished, indicating there existed a reversible charge transfer from DP NCs to MDMO-PPV polymers. Reversible charge transfer of Mn-doped DP NCs/MDMO-PPV nanocomposites was tuned by varying the excitation photon-energy. The manipulation of reversible charge transfer dynamics in the perovskite-polymer nanocomposites opens a new avenue for optical and optoelectronic applications.

All-Atom Nonadiabatic Semiclassical Mapping Dynamics for Photoinduced Charge Transfer of Organic Photovoltaic Molecules in Explicit Solvents.

Direct all-atom simulation of nonadiabatic dynamics in disordered condensed phases like liquid solutions and amorphous solids has been challenging. The first all-atom simulation of the photoinduced charge-transfer dynamics of a prototypical organic photovoltaic carotenoid-porphyrin-C60 molecular triad in explicit tetrahydrofuran is presented. Based on the Meyer-Miller mapping Hamiltonian, various semiclassical and mixed quantum-classical dynamics are employed, including the linearized semiclassical, symmetrical quasiclassical, mean-field Ehrenfest, classical mapping model, and spin-mapping model approaches. The all-atom nonadiabatic dynamics were compared to multi-state harmonic models with a globally shared bath, and the models built using the ensemble averages on the initial electronic state could reproduce the all-atom results. The solvent effect was found to be critical for the photoinduced charge transfer, and the time-dependent solute-solvent radial distribution functions revealed that only the nonadiabatic dynamics started with the effective forces on the initial electronic state could capture the correct nuclear dynamics. The proposed strategy for modeling condensed-phase nonadiabatic dynamics with atomistic details is readily applied to complex condensed-phase systems.

Deciphering Photoinduced Charge Transfer Dynamics in a Cross-Linked Graphene-Dye Nanohybrid.

The search for synthetic materials that mimic natural photosynthesis by converting solar energy into other more useful forms of energy is an ever-growing research endeavor. Graphene-based materials, with their exceptional electronic and optical properties, are exemplary candidates for high-efficiency solar energy harvesting devices. High photoactivity can be conveniently achieved by functionalizing graphene with small molecule organic semiconductors whose band-gaps can be tuned by structural modification, leading to interactions between the π-conjugated electronic systems in both the semiconductor and graphene. Here we investigate the ultrafast transient optical properties of a cross-linked graphene–dye (diphenyl-dithiophenediketopyrrolopyrrole) nanohybrid material, in which oligomers of the organic semiconductor dye are covalently bound to a random network of few-layer graphene flakes, and compare the results to those obtained for the reference dye monomer. Using a combination of ultrafast transient absorption and two-dimensional electronic spectroscopy, we provide substantial evidence for photoinduced charge transfer that occurs within 18 ps in the nanohybrid system. Notably, subpicosecond photoinduced torsional relaxation observed in the constituent dye monomer is absent in the cross-linked nanohybrid system. Through density functional theory calculations, we compare the competing effects of covalent bonding, increasing conjugation length, and the presence of multiple graphene flakes. We find evidence that the observed ultrafast charge transfer process occurs through a superexchange mechanism in which the oligomeric dye bridge provides virtual states enabling charge transfer between graphene–dye covalent bond sites.

Deciphering Photoinduced Charge Transfer Dynamics in a Cross-Linked Graphene–Dye Nanohybrid

Deciphering Photoinduced Charge Transfer Dynamics in a Cross-Linked Graphene–Dye Nanohybrid

Molecular Interface Engineering via Triazatruxene‐Based Moieties/NiOx as Hole‐Selective Bilayers in Perovskite Solar Cells for Reliability

Interface engineering is an effective approach to decrease nonradiative recombination and the energy barrier at the perovskite/hole transporting layer (HTL) interfaces. To overcome such limitations, an organic semiconductor (DTT‐EHDI 2 ) is proposed, which is, composed of dithienothiophene (DTT) as the core and a planar triazatruxene incorporating an alkyl chain as the side group. This is noted to be an effective interfacial layer for inverted planar perovskite solar cells (PSCs). The altered interface effectively minimizes the detrimental charge recombination and tailors the photoinduced charge transfer dynamics at the interface of the inorganic HTL/perovskite. The π‐conjugation in DTT‐EHDI 2 induces high hole mobility and electrical conductivity via electron‐donating properties and strong π–π intermolecular interaction. The synergetic approach leads to a substantial performance enhancement in dopant‐free DTT‐EHDI 2 ‐based inverted planar PSCs, achieving 18.15% power conversion efficiency with negligible hysteresis effect. The present approach provides an effective direction of the cost‐effective thiophene derivative as an interfacial agent to escalate the optoelectronic performances in photovoltaics.

Photoinduced Charge Transfer and Recombination Dynamics in Star Nonfullerene Organic Solar Cells.

Nonfullerene acceptors (NFAs) are regarded as star candidates for efficient organic solar cells with power conversion efficiency (PCE) over 18%. In contrast to the rapid development of NFA materials, however, the underlying excited-state dynamics which fundamentally govern the device performance remains unclear. In this Perspective, we discuss recent advances and provide our insights on photoinduced charge transfer and combination dynamics in NFA-based organic solar cells (OSCs), including the biphasic hole-transfer process and its correlation with morphology, the role of driving force and Marcus normal region behavior on interfacial hole-transfer properties, and charge recombination energy loss by NFA triplet formation. We also discuss our understanding of how to control the charge-transfer and recombination processes by phase morphology and molecular design to improve OSC performance. Finally, we suggest a few research directions, including the interfacial charge transfer and separation mechanism, the origin of low fill factor, and complex excited-state dynamics in multicomponent OSCs.

Intramolecular Photoinduced Charge Transfer and Recombination Dynamics in Vinylarene Terminated Organosilanes.

We report on charge-transfer dynamics of newly designed acceptor-donor-acceptor organosilanes, with a specific focus on how donor-acceptor combination and local chemical environment can be used to control the lifetime for intramolecular charge-separation between silane electron donors and organic acceptors. In this work linear oligosilanes were capped with arene-vinyl end groups of variable electron-accepting strength: weak (diester vinyl), intermediate (ester,cyano vinyl), and strong (dicyanovinyl). Ultrafast transient absorption spectroscopy was used to characterize their structure-dependent charge-transfer and recombination behaviors. All structures exhibit similar photoinduced ultrafast spectral dynamics that we ascribe to relaxation of the nascent charge-separated excited state followed by a return to the ground state via charge recombination. We find that relaxation of the nascent "hot" charge-separated excited state scales with the strength of dipole-dipole interactions between solvent molecules and the polar arene-vinyl acceptor. Furthermore, electron-accepting strength governs whether electronic coupling dictates charge recombination rate: weak acceptors produce charge-separated states that exhibit relatively large electronic coupling for back-electron transfer (approaching the adiabatic limit) that result in fast recombination, whereas the strong and moderate-strength acceptors support more stable charge-separated states with weaker coupling and longer lifetimes. We find that recombination rates increase substantially for structures with weak and moderate-strength acceptors in cyclohexane (i.e., negligible solvent reorganization energy), which we attribute to an increased electronic coupling in a nonpolar solvent environment where charge pairs are weakly screened. In contrast, for structures with strong electron acceptors, the very low reorganization energy of cyclohexane places back-electron transfer even further into the Marcus inverted regime, with a resultant increase in charge-separation lifetime. Together these results provide critical insights on how to tune photoinduced charge-transfer behavior in organic-inorganic hybrids that have potential material applications in molecular electronics and optoelectronics.

1T-rich 2D-WS2 as Interfacial Agent to Escalate Photo-induced Charge Transfer Dynamics in a Dopant-free Perovskite Solar Cells

1T-rich 2D-WS2 as Interfacial Agent to Escalate Photo-induced Charge Transfer Dynamics in a Dopant-free Perovskite Solar Cells

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.

Direct Nonadiabatic Simulations of the Photoinduced Charge Transfer Dynamics.

We apply direct nonadiabatic dynamics simulations to investigate photoinduced charge transfer reactions. Our approach is based on the mixed quantum-classical fewest switches surface hopping (FSSH) method that treats the transferring electron through time-dependent density functional theory and the nuclei classically. The photoinduced excited state is modeled as a transferring single-electron that initially occupies the LUMO of the donor molecule/moiety. This single-particle electronic wave function is then propagated quantum mechanically by solving the time-dependent Schrödinger equation in the basis of the instantaneous molecular orbitals (MOs) of the entire system. The nonadiabatic transitions among electronic states are modeled using the FSSH approach within the classical-path approximation. We apply this approach to simulate the photoinduced charge transfer dynamics in a few well-characterized molecular systems. Our results are in excellent agreement with both the experimental measurements and high-level (yet expensive) theoretical results.

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.