Femtosecond Time-resolved Absorption Spectroscopy Research Articles

(Invited) Charge Separation Processes in Non-Fullerene Acceptors Studied by Time-Resolved IR

The mechanism of charge transfer and charge dissociation processes are investigated by femtosecond time-resolved IR absorption spectroscopy.

Ultrafast Events of Photoexcited Iron(III) Chloride for Activation of Benzylic C-H Bonds.

The usage of rare-earth-metal catalysts in the synthesis of organic compounds is widespread in chemical industries but is limited owing to its environmental and economic costs. However, recent studies indicate that abundant-earth metals like iron(III) chloride can photocatalyze diverse organic transformations using blue-light LEDs. Still, the underlying mechanism behind such activity is debatable and controversial, especially in the absence of ultrafast spectroscopic results. To address this urgent challenge, we performed femtosecond time-resolved electronic absorption spectroscopy experiments of iron(III) chloride in selected organic solvents relevant to its photocatalytic applications. Our results show that the long-lived species [Fe(II) ← Cl•]* is primarily responsible for both oxidizing the organic substrate and reducing molecular oxygen through the diffusion process, leading to the final product and regenerating the photocatalyst rather than the most widely proposed free chloride radical (Cl•). Our study will guide the rational design of efficient earth-abundant photocatalysts.

Tracking nuclear motion in single-molecule magnets using femtosecond X-ray absorption spectroscopy

The development of new data storage solutions is crucial for emerging digital technologies. Recently, all-optical magnetic switching has been achieved in dielectrics, proving to be faster than traditional methods. Despite this, single-molecule magnets (SMMs), which are an important class of magnetic materials due to their nanometre size, remain underexplored for ultrafast photomagnetic switching. Herein, we report femtosecond time-resolved K-edge X-ray absorption spectroscopy (TR-XAS) on a Mn(III)-based trinuclear SMM. Exploiting the elemental specificity of XAS, we directly track nuclear dynamics around the metal ions and show that the ultrafast dynamics upon excitation of a crystal-field transition are dominated by a magnetically active Jahn-Teller mode. Our results, supported by simulations, reveal minute bond length changes from 0.01 to 0.05 Å demonstrating the sensitivity of the method. These geometrical changes are discussed in terms of magneto-structural relationships and consequently our results illustrate the importance of TR-XAS for the emerging area of ultrafast molecular magnetism.

Amplified Triplet Emission of Organic Periphery Groups by Exothermic Triplet-Triplet Energy Transfer from the 3MLCT State of an Ir(pmi)3 Core Complex to the 3LC State of Geometrically Confined Carbazole/Naphthyl Tethers.

To investigate the excited-state properties of metal-organic bichromophores, including energy transfer mechanisms, a series of new homoleptic N-heterocyclic carbene (NHC)-based iridium(III) complexes were prepared by incorporating a peripheral naphthalene (Np) (Ir(Nppmi)3: fac-/mer-Ir(1-Nppmi)3 and fac-/mer-Ir(2-Nppmi)3) or carbazole (Cz) (Ir(Czpmi)3: fac-/mer-Ir(o-Czpmi)3, fac-/mer-Ir(m-Czpmi)3, and fac-/mer-Ir(p-Czpmi)3) unit to the phenyl moiety of the phenylimidazole (pmi) ligand. Through a series of photophysical analyses and femtosecond time-resolved absorption (fs-TA) spectroscopy, it was discovered that the phosphorescence of the Ir core, (Ir(pmi)3), was considerably quenched, while intense phosphorescence peaks arising from the excited triplet Np (3Np*)/Cz (3Cz*) species were primarily observed at room temperature (r.t.) and low temperature. Such amplified phosphorescence of the tethered organic Np and Cz units originated from triplet-triplet energy transfer (TTET) from the high-lying metal-to-ligand charge transfer (3MLCT) state of the Ir(pmi)3 core to the ligand-centered triplet state (3LC) of the peripheral Np and Cz units. This result indicates that the exothermic intramolecular energy transfer (IET) in the excited triplet state realizes the efficient phosphorescent emission of geometrically confined organic tethers.

Effects of the Unique Chromophore-Protein Interactions on the Primary Photoreaction of Schizorhodopsin.

Schizorhodopsin (SzR) is a newly discovered microbial rhodopsin subfamily, functioning as an unusual inward-proton (H+) pump upon absorbing light. Two major protein structural differences around the chromophore have been found, resulting in unique chromophore-protein interactions that may be responsible for its unusual function. Therefore, it is important to elucidate how such a difference affects the primary photoreaction dynamics. We study the primary dynamics of SzR and its C75S mutant by femtosecond time-resolved absorption (TA) spectroscopy. The obtained TA data revealed that the photoisomerization in SzR proceeds more slowly and less efficiently than typical outward H+-pumping rhodopsins and that it further slows in the C75S mutant. We performed impulsive stimulated Raman measurements to clarify the effect of the cysteine residue on the retinal chromophore and found that interactions with Cys75 flatten the retinal chromophore of wild-type SzR. We discuss the effect of the unique chromophore-cysteine interaction on the retinal isomerization dynamics and structure of SzR.

Excited-State Dynamics of All the Mono-cis and the Major Di-cis Isomers of β-Apo-8'-Carotenal as Revealed by Femtosecond Time-Resolved Transient Absorption Spectroscopy.

Cis isomers of carotenoids play important roles in light harvesting and photoprotection in photosynthetic bacteria, such as the reaction center in purple bacteria and the photosynthetic apparatus in cyanobacteria. Carotenoids containing carbonyl groups are involved in efficient energy transfer to chlorophyll in light-harvesting complexes, and their intramolecular charge-transfer (ICT) excited states are known to be important for this process. Previous studies, using ultrafast laser spectroscopy, have focused on the central-cis isomer of carbonyl-containing carotenoids, revealing that the ICT excited state is stabilized in polar environments. However, the relationship between the cis isomer structure and the ICT excited state has remained unresolved. In this study, we performed steady-state absorption and femtosecond time-resolved absorption spectroscopy on nine geometric isomers (7-cis, 9-cis, 13-cis, 15-cis, 13'-cis, 9,13'-cis, 9,13-cis, 13,13'-cis, and all-trans) of β-apo-8'-carotenal, whose structures are well-defined, and discovered correlations between the decay rate constant of the S1 excited state and the S0-S1 energy gap, as well as between the position of the cis-bend and the degree of stabilization of the ICT excited state. Our results demonstrate that the ICT excited state is stabilized in polar environments in cis isomers of carbonyl-containing carotenoids and suggest that the position of the cis-bend plays an important role in the stabilization of the excited state.

Energy dissipation efficiency in the CP43 assembly intermediate complex of photosystem II

Photosystem II in oxygenic organisms is a large membrane bound rapidly turning over pigment protein complex. During its biogenesis, multiple assembly intermediates are formed, including the CP43-preassembly complex (pCP43). To understand the energy transfer dynamics in pCP43, we first engineered a His-tagged version of the CP43 in a CP47-less strain of the cyanobacterium Synechocystis 6803. Isolated pCP43 from this engineered strain was subjected to advanced spectroscopic analysis to evaluate its excitation energy dissipation characteristics. These included measurements of steady-state absorption and fluorescence emission spectra for which correlation was tested with Stepanov relation. Comparison of fluorescence excitation and absorptance spectra determined that efficiency of energy transfer from β-carotene to chlorophyll a is 39 %. Time-resolved fluorescence images of pCP43-bound Chl a were recorded on streak camera, and fluorescence decay dynamics were evaluated with global fitting. These demonstrated that the decay kinetics strongly depends on temperature and buffer used to disperse the protein sample and fluorescence decay lifetime was estimated in 3.2–5.7 ns time range, depending on conditions. The pCP43 complex was also investigated with femtosecond and nanosecond time-resolved absorption spectroscopy upon excitation of Chl a and β-carotene to reveal pathways of singlet excitation relaxation/decay, Chl a triplet dynamics and Chl a → β-carotene triplet state sensitization process. The latter demonstrated that Chl a triplet in the pCP43 complex is not efficiently quenched by carotenoids. Finally, detailed kinetic analysis of the rise of the population of β-carotene triplets determined that the time constant of the carotenoid triplet sensitization is 40 ns.

Photoionization of 3-Methylindole Embedded in Sodium Dodecyl Sulfate and Dodecyltrimethylammonium Chloride Micelles: Migration of Electrons Generated in Micelle Cores and Their Solvation in Outside Water

Electrons were generated in the core of micelles formed by negatively charged sodium dodecyl sulfate (SDS) or positively charged dodecyltrimethylammonium chloride (DTAC) by photoionization of 3-methylindole embedded in the core. The electrons were hydrated after they moved out of the core to the outer aqueous phase. These processes were monitored with femtosecond time-resolved absorption spectroscopy. The migration of electrons from the micelle core to the outer aqueous phase was faster than the instrumental response time of 200 fs. Hot electrons in the aqueous phase were produced in ≤320 fs. There was no significant difference observed for the micellar solutions of negatively charged SDS and positively charged DTAC, or for water. The geminate recombination between the electrons and the radical cations was hindered to a large extent once the electrons hydrated at the outer aqueous phase were separated from the radical cations remaining in the micelle core.

Unifying Perspective of the Ultrafast Photodynamics of Orange Carotenoid Proteins from Synechocystis: Peril of High-Power Excitation, Existence of Different S* States, and Influence of Tagging.

A substantial number of Orange Carotenoid Protein (OCP) studies have aimed to describe the evolution of singlet excited states leading to the formation of a photoactivated form, OCPR. The most recent one suggests that 3 ps-lived excited states are formed after the sub-100 fs decay of the initial S2 state. The S* state, which has the longest reported lifetime of a few to tens of picoseconds, is considered to be the precursor of the first red photoproduct P1. Here, we report the ultrafast photodynamics of the OCP from Synechocystis PCC 6803 carried out using visible–near infrared femtosecond time-resolved absorption spectroscopy as a function of the excitation pulse power and wavelength. We found that a carotenoid radical cation can form even at relatively low excitation power, obscuring the determination of photoactivation yields for P1. Moreover, the comparison of green (540 nm) and blue (470 nm) excitations revealed the existence of an hitherto uncharacterized excited state, denoted as S∼, living a few tens of picoseconds and formed only upon 470 nm excitation. Because neither the P1 quantum yield nor the photoactivation speed over hundreds of seconds vary under green and blue continuous irradiation, this S∼ species is unlikely to be involved in the photoactivation mechanism leading to OCPR. We also addressed the effect of His-tagging at the N- or C-termini on the excited-state photophysical properties. Differences in spectral signatures and lifetimes of the different excited states were observed at a variance with the usual assumption that His-tagging hardly influences protein dynamics and function. Altogether our results advocate for the careful consideration of the excitation power and His-tag position when comparing the photoactivation of different OCP variants and beg to revisit the notion that S* is the precursor of photoactivated OCPR.

Internal electric field engineering step-scheme–based heterojunction using lead-free Cs3Bi2Br9 perovskite–modified In4SnS8 for selective photocatalytic CO2 reduction to CO

This study focuses on improving photocatalytic CO2 reduction reaction (CRR) activity and modulating product selectivity. An In4SnS8/Cs3Bi2Br9-X (ISS/CBB-X) heterojunction is prepared using novel lead-free Cs3Bi2Br9 perovskite quantum dot–modified In4SnS8, which shows considerable potential as photocatalysts for CRRs under visible light. The optimised ISS/CBB photocatalyst exhibits high activity and CO selectivity with a CO yield and selectivity of 9.55 μmol g−1 h−1 and 92.9%, respectively, 3.8 and 1.5 times higher than those of pristine ISS, respectively. Moreover, the step-scheme (S-scheme) mechanism can be fully confirmed via in situ irradiated X-ray photoelectron spectroscopy, in situ electron spin resonance, femtosecond time-resolved absorption spectroscopy and density functional theory calculations. Based on in situ diffuse reflectance spectra and theoretical investigations, the ISS/CBB shows a decreased energy barrier towards CO2 reduction to CO through an adsorbed ⁕COOH intermediate. This study contributes to the further understanding of fabricating efficient S-scheme-based photocatalysts for selective CRR.

Dynamics of electron ejection on photoionization of trans-stilbene and biphenyl in acetonitrile as observed with femtosecond time-resolved near-IR absorption spectroscopy.

Photoionization in solution is a basic but complex phenomenon involving a solute, an ejected electron and surrounding solvent molecules. It may seem obvious that an electron is released immediately after the parent molecule is excited to an electronic state that directly leads to the electron dissociation. However, it has been reported that the radical cations are formed in 17 ps, 24 ps, and 38 ps for trans-stilbene and 20 ps for biphenyl, based on time-resolved Raman and visible absorption measurements. For understanding this intriguing phenomenon, we observe the solvation process of electrons ejected from trans-stilbene and biphenyl with femtosecond time-resolved near-IR spectroscopy covering 900 to 1550 nm. We find that the near-IR absorption signals of the ejected electrons rise in 0.28 ± 0.01 ps for trans-stilbene and 0.33 ± 0.04 ps for biphenyl. The parent molecules release electrons in about 0.3 ps, not in a few tens of picoseconds, after the photoirradiation. The delayed appearance of the radical cation signals strongly suggests that the radical cation is formed initially in a highly excited state, electronically and vibrationally, that would not give a clear signal of Raman or absorption transitions. It then relaxes to the radical ground state in a few tens of picoseconds. We clarify the electron dissociation process associated with the photoionization of aromatic molecules with fast time-resolved spectroscopy.

A Unified View on Varied Ultrafast Dynamics of the Primary Process in Microbial Rhodopsins.

All-trans to 13-cis photoisomerization of the protonated retinal Schiff base (PRSB) chromophore is the primary step that triggers various biological functions of microbial rhodopsins. While this ultrafast primary process has been extensively studied, it has been recognized that the relevant excited-state relaxation dynamics differ significantly from one rhodopsin to another. To elucidate the origin of the complicated ultrafast dynamics of the primary process in microbial rhodopsins, we studied the excited-state dynamics of proteorhodopsin, its D97N mutant, and bacteriorhodopsin by femtosecond time-resolved absorption (TA) spectroscopy in a wide pH range. The TA data showed that their excited-state relaxation dynamics drastically change when pH approaches the pKa of the counterion residue of the PRSB chromophore in the ground state. This result reveals that the varied excited-state relaxation dynamics in different rhodopsins mainly originate from the difference of the ground-state heterogeneity (i.e., protonation/deprotonation of the PRSB counterion).

Solvation Dynamics of Wet Ethaline: Water is the Magic Component.

The past two decades witnessed the development of a new type of solvent system, named deep eutectic solvents, which have become increasingly investigated because they offer new and potentially favorable properties, such as wide tunability in electrochemical, mechanical, and transport properties. Deep eutectic solvent (DES) systems are composed of at least one main solvent and an additional component that is meant to interrupt the original solvent/solvent interactions, thereby introducing lower melting points relative to each individual component. Ethaline (a 1:2 mol % mixture of choline chloride and ethylene glycol) is one of the most promising DES systems. However, it is also known to be very hygroscopic, which is a constant concern because water absorption during the use of ethaline alters its properties. Within this work, we demonstrate that modest amounts of water addition (1-10%) to ethaline are of little concern for practical use and can even lead to performance improvements, such as accelerated relaxation and solvation. In contrast, very small amounts of <1% of water lead to additional slowing of the solvent response. Thus, we suggest that the attempt to dry ethaline below 1% moisture is rather counterproductive if one attempts to achieve effective solvation and charge transport properties from DESs. This study investigates the effect of water content on the diffusional relaxation dynamics of ethaline. A set of independent spectroscopic experiments and computational simulations are aimed to provide insight into the solvent response of the DES system using femtosecond time-resolved absorption spectroscopy (fs-TA), broadband dielectric spectroscopy (BDS), nuclear magnetic resonance (NMR) diffusometry and broadband relaxometry, and molecular dynamics simulations (MDS) on ethaline with 0, 0.1, 1, 10, and 28.5 wt % added water. For dry ethaline, we identify choline chloride as the rate-limiting solvation component in ethaline. However, the role of the solvent components changes gradually as water is added. We provide quantitative solvent relaxation rates using the different presented time-resolved spectroscopic techniques and find remarkable agreement between them. Based on the solvent relaxation rates and combined with MDS, we develop a molecular understanding of the individual solvent components and their interactions in dry and wet ethaline with varying amounts of water content.

Time resolved study of carrier relaxation dynamics in α-Al2O3

The relaxation of excited carriers in α–Al2O3 is complex, depending for instance on the type of ionizing radiation. Using femtosecond time-resolved absorption spectroscopy, we can induce a controllable excitation density on a wide range, and follow the relaxation dynamics from 30 fs to 7 ns. We show that the excited carrier decay is non-exponential: it is dependent on the pump intensity, i.e. on the initial carrier concentration. We describe the relaxation as a two-steps process, involving the trapping of initially free electron–hole pairs, followed by recombination. A numerical model taking into account the initial electronic excitation by multiphoton absorption and the subsequent relaxation allows to quantitatively reproduce the amplitude of the measured absorption and its temporal evolution.

Role of hydrogen bond alternation and charge transfer states in photoactivation of the Orange Carotenoid Protein

Here, we propose a possible photoactivation mechanism of a 35-kDa blue light-triggered photoreceptor, the Orange Carotenoid Protein (OCP), suggesting that the reaction involves the transient formation of a protonated ketocarotenoid (oxocarbenium cation) state. Taking advantage of engineering an OCP variant carrying the Y201W mutation, which shows superior spectroscopic and structural properties, it is shown that the presence of Trp201 augments the impact of one critical H-bond between the ketocarotenoid and the protein. This confers an unprecedented homogeneity of the dark-adapted OCP state and substantially increases the yield of the excited photoproduct S*, which is important for the productive photocycle to proceed. A 1.37 Å crystal structure of OCP Y201W combined with femtosecond time-resolved absorption spectroscopy, kinetic analysis, and deconvolution of the spectral intermediates, as well as extensive quantum chemical calculations incorporating the effect of the local electric field, highlighted the role of charge-transfer states during OCP photoconversion.

Interface engineering Z-scheme Ti-Fe2O3/In2O3 photoanode for highly efficient photoelectrochemical water splitting

Exploiting interface-engineer of In2O3-based photoanode to achieve a higher charge separation efficiency could be regarded as a pivotal but challenging research in water splitting. Herein, the state-of-the-art Ti-Fe2O3/In2O3 photoanodes with different Ti4+ doping concentrations are fabricated for exploring the interface-engineering effect on PEC performance. The optimized 150Ti-Fe2O3/In2O3 photoelectrode with the rapid interfacial hole trapped (∼ 8.96 ps) and long-lived charge separation states could achieve excellent PEC performance by femtosecond time-resolved absorption spectroscopy (fs-TAS). As expected, it shows the highest photocurrent density of 2 mA/cm2 at 1.23 V vs. RHE, which is nearly 7 times higher compared with pure In2O3. Moreover, the Z-scheme mechanism could be fully confirmed by femtosecond time-resolved absorption spectroscopy (fs-TAS) and in-situ double-beam detection strategy (AM 1.5 + 405 nm). This work provides an effective and feasible strategy on designing and regulating high-efficiency composite photoanode with Z-scheme transfer mechanism.

Structure tracking of nuclear wave packet oscillations by femtosecond time-resolved X-ray absorption spectroscopy

Progress in technology in recent decades has brought not only huge leaps in our knowledge across many fields, but has also led to the development of new tools that help and support the pursuit of such knowledge. Spectroscopy, the study of the interaction between matter and electromagnetic radiation, is used in chemistry, physics, astronomy and other fields, and allows scientists to investigate the physical and electronic structure as well as composition of materials. A number of techniques, including X-ray spectroscopy, have been developed to detect and measure materials in this way. Dr Tetsuo Katayama, from the Japan Synchrotron Radiation Research Institute (JASRI), is part of a team furthering research in this field.

Femtosecond time-resolved spectroscopic observation of long-lived charge separation in bimetallic sulfide/g-C3N4 for boosting photocatalytic H2 evolution

Copper-nickel sulfides could effectively suppress deep trapping states of active charge in carbon nitride. It also improves the efficiency of the shallow trapped electron transfer through CS bond for enhancing visible-light-driven photocatalytic hydrogen production with rates up to 752.8 μmol h−1 g−1, that is 470 times higher than that of pristine g-C3N4 (1.6 μmol h−1 g−1) so far. The kinetic coupling of electron transfer and long-lived charge separation (∼ 4896 ps) are systematically investigated by femtosecond time-resolved absorption spectroscopy (fs-TA). The TA signal of the composite is quenched by hole sacrificial agent, assigning to the effective hole extraction for high photocatalytic activity. Furthermore, a remarkable near-infrared-driven photocatalytic H2 evolution (0.32 μmol h−1 g−1, λ > 800 nm) was achieved due to the hole transfer from copper-nickel sulfide to the trap state of g-C3N4, indicating that the strong interaction between copper-nickel sulfide and g-C3N4 is favorable to charge transfer and long-lived charge separation states.

Simulation of time-resolved x-ray absorption spectroscopy of ultrafast dynamics in particle-hole-excited 4-(2-thienyl)-2,1,3-benzothiadiazole.

To date, alternating co-polymers based on electron-rich and electron-poor units are the most attractive materials to control functionality of organic semiconductor layers in which ultrafast excited-state processes play a key role. We present a computational study of the photoinduced excited-state dynamics of the 4-(2-thienyl)-2,1,3-benzothiadiazole (BT-1T) molecule, which is a common building block in the backbone of π-conjugated polymers used for organic electronics. In contrast to homo-polymer materials, such as oligothiophene, BT-1T has two non-identical units, namely, thiophene and benzothiadiazole, making it attractive for intramolecular charge transfer studies. To gain a thorough understanding of the coupling of excited-state dynamics with nuclear motion, we consider a scenario based on femtosecond time-resolved x-ray absorption spectroscopy using an x-ray free-electron laser in combination with a synchronized ultraviolet femtosecond laser. Using Tully's fewest switches surface hopping approach in combination with excited-state calculations at the level of configuration interaction singles, we calculate the gas-phase x-ray absorption spectrum at the carbon and nitrogen K edges as a function of time after excitation to the lowest electronically excited state. The results of our time-resolved calculations exhibit the charge transfer driven by non-Born-Oppenheimer physics from the benzothiadiazole to thiophene units during relaxation to the ground state. Furthermore, our ab initio molecular dynamics simulations indicate that the excited-state relaxation processes involve bond elongation in the benzothiadiazole unit as well as thiophene ring puckering at a time scale of 100 fs. We show that these dynamical trends can be identified from the time-dependent x-ray absorption spectrum.

A dominant factor of the cycloreversion reactivity of diarylethene derivatives as revealed by femtosecond time-resolved absorption spectroscopy.

Dynamics of the cycloreversion reaction of a photochromic diarylethene derivative with a small ring-opening reaction yield (∼1%) was investigated by using femtosecond transient absorption spectroscopy. The reaction rate constant and activation barrier on the reaction coordinate were quantitatively analyzed on the basis of the temperature and excitation wavelength dependencies of the reaction yield and excited state dynamics. From the comparison of the present results with those in a more reactive derivative, we concluded that a key factor regulating the overall reaction yield is the branching ratio at the conical intersection where the excited state population is split into the product and the initial reactant. The excitation wavelength dependence of the dynamics indicated that the geometrical relaxation and vibrational cooling proceed in a few picosecond time scale behind the cycloreversion process, and the vibrational excess energy assists the molecule to climb up the energy barrier.