Time-domain Raman Spectroscopy Research Articles

Boosting the Brightness of Raman Tags Using Cyanostar Macrocycles.

Raman probes have received growing attention for their potential use in super-multiplex biological imaging and flow cytometry applications that cannot be achieved using fluorescent probes. However, obtaining strong Raman scattering signals from small Raman probes has posed a challenge that holds back their practical implementation. Here, we present new types of Raman-active nanoparticles (Rdots) that incorporate ionophore macrocycles, known as cyanostars, to act as ion-driven and structure-directing spacers to address this problem. These macrocycle-enhanced Rdots (MERdots) exhibit sharper and higher electronic absorption peaks than Rdots. When combined with resonant broadband time-domain Raman spectroscopy, these MERdots show a ∼3-fold increase in Raman intensity compared to conventional Rdots under the same particle concentration. Additionally, the detection limit on the concentration of MERdots is improved by a factor of 2.5 compared to that of Rdots and a factor of 430 compared to that of Raman dye molecules in solution. The compact size of MERdots (26 nm in diameter) and their increased Raman signal intensity, along with the broadband capabilities of time-domain resonant Raman spectroscopy, make them promising candidates for a wide range of biological applications.

Photoexcited Plasmon-Driven Ultrafast Dynamics of the Adsorbate Probed by Femtosecond Time-Resolved Surface-Enhanced Time-Domain Raman Spectroscopy.

Metal nanoparticles have high potential in light-harvesting applications by transferring absorbed photon energy to the adsorbates. However, photoexcited plasmon-driven ultrafast dynamics of the adsorbate on metal nanoparticles have not been clearly understood. We studied ultrafast plasmon-driven processes of trans-1,2-bis(4-pyridyl)ethylene (BPE) adsorbed on gold nanoparticle assemblies (GNAs) using time-resolved surface-enhanced impulsive stimulated Raman spectroscopy (TR-SE-ISRS). After photoexciting the localized surface plasmon resonance (LSPR) band of the GNAs, we measured femtosecond time-resolved surface-enhanced Raman spectra of the adsorbate, which exhibited transient bleach in the Raman signal and following biphasic recovery that proceeds on the time scale of a few tens of picoseconds. The TR-SE-ISRS data were analyzed with singular value decomposition, and the obtained species-associated Raman spectra indicated that photoexcitation of the LSPR band alters chemical interaction between BPE and the GNAs on an ultrafast time scale; initial steady-state BPE is recovered through a precursor state that has weaker interaction with the GNAs.

Inside Cover: Real‐time Observation of Structural Dynamics Triggering Excimer Formation in a Perylene Bisimide Folda‐dimer by Ultrafast Time‐Domain Raman Spectroscopy (Angew. Chem. Int. Ed. 13/2022)

The excimer (a contraction of the excited-state dimer) is the most classical photoproduct which has been generally regarded as a trap site. In their Research Article (202114474), Hyungjun Kim, Frank Würthner, Dongho Kim and co-workers have captured the vibrational snapshots triggering the excimer formation and relaxation processes of the perylene bisimide folda-dimer using the ultrafast time-domain Raman spectroscopy. Understanding the mechanism of the excimer provides important criteria for designing the π-conjugated organic molecules.

Real-time Observation of Structural Dynamics Triggering Excimer Formation in a Perylene Bisimide Folda-dimer by Ultrafast Time-Domain Raman Spectroscopy.

In π‐conjugated organic photovoltaic materials, an excimer state has been generally regarded as a trap state which hinders efficient excitation energy transport. But despite wide investigations of the excimer for overcoming the undesirable energy loss, the understanding of the relationship between the structure of the excimer in stacked organic compounds and its properties remains elusive. Here, we present the landscape of structural dynamics from the excimer formation to its relaxation in a co‐facially stacked archetypical perylene bisimide folda‐dimer using ultrafast time‐domain Raman spectroscopy. We directly captured vibrational snapshots illustrating the ultrafast structural evolution triggering the excimer formation along the interchromophore coordinate on the complex excited‐state potential surfaces and following evolution into a relaxed excimer state. Not only does this work showcase the ultrafast structural dynamics necessary for the excimer formation and control of excimer characteristics but also provides important criteria for designing the π‐conjugated organic molecules.

Tracking Ultrafast Structural Dynamics by Time-Domain Raman Spectroscopy.

In traditional Raman spectroscopy, narrow-band light is irradiated on a sample, and its inelastic scattering, i.e., Raman scattering, is detected. The energy difference between the Raman scattering and the incident light corresponds to the vibrational energy of the molecule, providing the Raman spectrum that contains rich information about the molecular-level properties of the materials. On the other hand, by using ultrashort optical pulses, it is possible to induce Raman-active coherent nuclear motion of the molecule and to observe the molecular vibration in real time. Moreover, this time-domain Raman measurement can be combined with femtosecond photoexcitation, triggering chemical changes, which enables tracking ultrafast structural dynamics in a form of “time-resolved” time-domain Raman spectroscopy, also known as time-resolved impulsive stimulated Raman spectroscopy. With the advent of stable, ultrashort laser pulse sources, time-resolved impulsive stimulated Raman spectroscopy now realizes high sensitivity and a wide detection frequency window from THz to 3000 cm–1, and has seen success in unveiling the molecular mechanisms underlying the efficient functions of complex molecular systems. In this Perspective, we overview the present status of time-domain Raman spectroscopy, particularly focusing on its application to the study of femtosecond structural dynamics. We first explain the principle and a brief history of time-domain Raman spectroscopy and then describe the apparatus and recent applications to the femtosecond dynamics of complex molecular systems, including proteins, molecular assemblies, and functional materials. We also discuss future directions for time-domain Raman spectroscopy, which has reached a status allowing a wide range of applications.

Femtosecond Structural Dynamics of Complex Molecular Systems Studied by Time-Domain Raman Spectroscopy Using Few-Cycle Pulses

Femtosecond Structural Dynamics of Complex Molecular Systems Studied by Time-Domain Raman Spectroscopy Using Few-Cycle Pulses

Tracking Photoinduced Au-Au Bond Formation through Transient Terahertz Vibrations Observed by Femtosecond Time-Domain Raman Spectroscopy.

Real-time observation of chemical bond formation and subsequent nuclear rearrangements is an ultimate goal of chemical science. Yet, such attempts have been hampered by the technical difficulty of triggering bond formation at well-defined, desired timing. The trimer of dicyanoaurate complex ([Au(CN)2-]3) is an ideal system for achieving this aim because the tight covalent Au-Au bonds are formed upon photoexcitation. Despite the apparent simplicity of the system, however, recent time-resolved studies failed to construct a consistent picture of its ultrafast dynamics. Here, we report femtosecond time-domain Raman tracking of ultrafast structural dynamics of the [Au(CN)2-] trimer upon photoinduced Au-Au bond formation. The obtained Raman data reveal that the Au-Au breathing vibration at ∼90 cm-1 exhibits a gradual frequency upshift in a few picoseconds, demonstrating a continuous bent-to-linear structural change on the triplet-state potential energy surface upon the Au-Au bond formation. The comprehensive ultrafast spectroscopic study settles the controversy on this prototypical molecular assembly.

Sagnac-enhanced impulsive stimulated Raman scattering for highly sensitive low-frequency Raman spectroscopy.

The "fingerprint" (500-1800 cm-1) and "high-frequency" (2400-4000 cm-1) regions in Raman spectroscopy are commonly used for label-free chemical analysis, while the "low-frequency" region (<200 cm-1) is often overlooked, despite containing rich information. This is largely due to the challenge of measuring weak Raman signals that are obscured by strong Rayleigh scattering. Here we propose and experimentally demonstrate Sagnac-enhanced impulsive stimulated Raman scattering (SE-ISRS), a filter-free method for time-domain Raman spectroscopy that overcomes the challenge and provides low-frequency Raman spectra at all probe frequencies. Using SE-ISRS for simultaneous low-frequency and fingerprint region measurements, we demonstrate a >5× enhancement of the signal-to-noise ratio compared to conventional ISRS spectroscopy.

A molecular movie of ultrafast singlet fission

The complex dynamics of ultrafast photoinduced reactions are governed by their evolution along vibronically coupled potential energy surfaces. It is now often possible to identify such processes, but a detailed depiction of the crucial nuclear degrees of freedom involved typically remains elusive. Here, combining excited-state time-domain Raman spectroscopy and tree-tensor network state simulations, we construct the full 108-atom molecular movie of ultrafast singlet fission in a pentacene dimer, explicitly treating 252 vibrational modes on 5 electronic states. We assign the tuning and coupling modes, quantifying their relative intensities and contributions, and demonstrate how these modes coherently synchronise to drive the reaction. Our combined experimental and theoretical approach reveals the atomic-scale singlet fission mechanism and can be generalized to other ultrafast photoinduced reactions in complex systems. This will enable mechanistic insight on a detailed structural level, with the ultimate aim to rationally design molecules to maximise the efficiency of photoinduced reactions.

Fifth-order time-domain Raman spectroscopy of photoactive yellow protein for visualizing vibrational coupling in its excited state.

We report fifth-order time-domain Raman spectroscopy of photoactive yellow protein (PYP), with the aim to visualize vibrational coupling in its excited state. After the ultrashort actinic pump pulse prepared the vibrational coherence and population in the excited state, the evolving vibrational structure was tracked by time-resolved impulsive stimulated Raman spectroscopy using sub-7-fs pulses. The obtained fifth-order time-domain Raman data were translated to a two-dimensional (2D) frequency-frequency correlation map, which visualizes the correlation between low- and high-frequency vibrational modes of the excited state. The 2D map of PYP reveals a cross peak, indicating the coupling between the phenolic C─O stretch mode of the chromophore and the low-frequency modes (~160 cm-1), assignable to the intermolecular motions involving the surrounding hydrogen-bonded amino acids. The unveiled coupling suggests the importance of the low-frequency vibrational motion in the primary photoreaction of PYP, highlighting the unique capability of this spectroscopic approach for studying ultrafast reaction dynamics.

Excited-state vibrational dynamics toward the polaron in methylammonium lead iodide perovskite

Hybrid organic–inorganic perovskites have attractive optoelectronic properties including exceptional solar cell performance. The improved properties of perovskites have been attributed to polaronic effects involving stabilization of localized charge character by structural deformations and polarizations. Here we examine the Pb–I structural dynamics leading to polaron formation in methylammonium lead iodide perovskite by transient absorption, time-domain Raman spectroscopy, and density functional theory. Methylammonium lead iodide perovskite exhibits excited-state coherent nuclear wave packets oscillating at ~20, ~43, and ~75 cm−1 which involve skeletal bending, in-plane bending, and c-axis stretching of the I–Pb–I bonds, respectively. The amplitudes of these wave packet motions report on the magnitude of the excited-state structural changes, in particular, the formation of a bent and elongated octahedral PbI64− geometry. We have predicted the excited-state geometry and structural changes between the neutral and polaron states using a normal-mode projection method, which supports and rationalizes the experimental results. This study reveals the polaron formation via nuclear dynamics that may be important for efficient charge separation.

Probing the early stages of photoreception in photoactive yellow protein with ultrafast time-domain Raman spectroscopy.

Unveiling the nuclear motions of photoreceptor proteins in action is a crucial goal in protein science in order to understand their elaborate mechanisms and how they achieve optimal selectivity and efficiency. Previous studies have provided detailed information on the structures of intermediates that appear during the later stages (>ns) of such photoreception cycles, yet the initial events immediately after photoabsorption remain unclear because of experimental challenges in monitoring nuclear rearrangements on ultrafast timescales, including protein-specific low-frequency motions. Using time-domain Raman probing with sub-7-fs pulses, we obtain snapshot vibrational spectra of photoactive yellow protein and a mutant with high sensitivity, providing insights into the key responses that drive photoreception. Our data show a drastic intensity drop of the excited-state marker band at 135 cm-1 within a few hundred femtoseconds, suggesting a rapid weakening of the hydrogen bond that anchors the chromophore. We also track formation of the first ground-state intermediate over the first few picoseconds and fully characterize its vibrational structure, revealing a substantially-twisted cis conformation.

Hydroxide Hydrogen Bonding: Probing the Solvation Structure through Ultrafast Time Domain Raman Spectroscopy.

The mechanism of charge transport in aqueous media is critical in molecular, materials, and life sciences. The structure of the solvated hydroxide ion has been an area of some controversy. Polarization-resolved ultrafast time domain polarizability relaxation is used here to resolve the terahertz frequency Raman spectrum of hydroxide solutions. The measurements reveal the totally symmetric hydrogen-bond stretching (HO(-)···HOH) mode of the solvated hydroxide, permitting an experimental measurement of the bond force constant. The observed polarized Raman spectra are compared with those obtained from DFT calculations performed on HO(-)(H2O)n clusters. Good agreement between the observed frequency and the polarization dependence is found for the n = 3 or 4 clusters, particularly for those in which the solvating water molecules adopt a planar structure. The frequency of the symmetric stretch increases with concentration, consistent with an effect of ionic strength on either the H-bond or the structure of the cluster.

Measuring acetic acid dimer modes by ultrafast time-domain Raman spectroscopy

Acetic acid is capable of forming strong multiple hydrogen bonds and therefore different dimeric H-bonded structures in neat liquid phase and in solutions. The low frequency Raman spectra of acetic acid (neat, in aqueous solution and as a function of temperature) were obtained by ultrafast time and polarization resolved optical Kerr effect (OKE) measurements. Isotropic OKE measurements clearly reveal a specific totally symmetric mode related to the dimeric structure H-bond stretching mode. The effects of isotope substitution, water dilution and temperature on this mode were investigated. These results together with anisotropic OKE measurements and density functional theory calculations for a number of possible dimers provide strong evidence for the cyclic dimer structure being the main structure in liquid phase persisting down to acetic acid concentrations of 10 M. Some information about the dimer structure and concentration dependence was inferred.

Vibrations at Liquid-liquid and Air-Solid Interfaces measured by Interface-Specific Time-Domain Raman Spectroscopy

Vibrations at Liquid-liquid and Air-Solid Interfaces measured by Interface-Specific Time-Domain Raman Spectroscopy

Low-frequency vibrations of molecular submonolayers detected by time-domain Raman spectroscopy

Time-domain Raman spectroscopy using a single color pump-probe technique was performed to observe low-frequency vibrations of a submonolayer (4×1013 molecules cm−2) film of cresyl violet on a fused-silica surface. A16-fs pump pulse at 650nm created Raman-active nuclear motions (vibrational coherence) in the film. The vibrational coherence was monitored as the time-dependent reflectance change of the sample. This time-domain method is promising for sensitive detection of low-frequency (terahertz) Raman bands of molecular submonolayer films, especially when the films contain highly luminescent compounds.

Time-Resolved Impulsive Stimulated Raman Studies of 1,1‘-Binaphthyl in the Excited State: Low-Frequency Vibrations and Conformational Relaxation

The conformational relaxation of excited-state 1,1‘-binaphthyl in solution was investigated by using femtosecond time-resolved absorption and time-resolved time-domain Raman spectroscopy. Femtosecond time-resolved absorption measurements confirmed that the first transient (the “unrelaxed” S1 state) is generated in a subpicosecond time scale after photoexcitation and that it undergoes a relaxation with a time constant of 16 ps (in cyclohexane) to form the second transient (the “relaxed” S1 state). Time-domain Raman experiments provided low-frequency Raman data of the relaxed S1 state for the frequency region of 0−400 cm-1. The obtained Raman data of the relaxed S1 state were significantly different from the low-frequency S0 spectrum in solution. The relaxed S1 spectrum resembles the spectrum of the crystalline form that has a dihedral angle of 69°, whereas the S0 Raman spectrum in solution coincides well with that of the crystalline form having a dihedral angle of 103°. The time-domain Raman measurements p...

Polarization-selective femtosecond Raman spectroscopy of low-frequency motions in hydrated protein films

We investigated the vibrational dynamics of proteins in amorphous hydrated films of lysozyme and myoglobin using polarization-selective time-domain Raman spectroscopy. The anisotropic spectra for these proteins all have a broad peak due to librational motion of side chains at 90 cm −1 and a background that may arise from bound water. The isotropic spectrum of lysozyme is similar to that of myoglobin, and has peaks at 240 and 500 cm −1 that are likely due to secondary structure fluctuations. These results suggest that low-frequency deformations of the protein molecule may contribute to the solvation dynamics of proteins in aqueous solution.