Sangwoon Yoon

Structural Observation of the Primary Isomerization in Vision with Femtosecond-Stimulated Raman

The primary event that initiates vision is the light-induced 11-cis to all-trans isomerization of retinal in the visual pigment rhodopsin. Despite decades of study with the traditional tools of chemical reaction dynamics, both the timing and nature of the atomic motions that lead to photoproduct production remain unknown. We used femtosecond-stimulated Raman spectroscopy to obtain time-resolved vibrational spectra of the molecular structures formed along the reaction coordinate. The spectral evolution of the vibrational features from 200 femtoseconds to 1 picosecond after photon absorption reveals the temporal sequencing of the geometric changes in the retinal backbone that activate this receptor.

Femtosecond broadband stimulated Raman spectroscopy: Apparatus and methods

The laser, detection system, and methods that enable femtosecond broadband stimulated Raman spectroscopy (FSRS) are presented in detail. FSRS is a unique tool for obtaining high time resolution (<100 fs) vibrational spectra with an instrument response limited frequency resolution of <10 cm(-1). A titanium:Sapphire-based laser system produces the three different pulses needed for FSRS: (1) A femtosecond visible actinic pump that initiates the photochemistry, (2) a narrow bandwidth picosecond Raman pump that provides the energy reservoir for amplification of the probe, and (3) a femtosecond continuum probe that is amplified at Raman resonances shifted from the Raman pump. The dependence of the stimulated Raman signal on experimental parameters is explored, demonstrating the expected exponential increase in Raman intensity with concentration, pathlength, and Raman pump power. Raman spectra collected under different electronic resonance conditions using highly fluorescent samples highlight the fluorescence rejection capabilities of FSRS. Data are also presented illustrating our ability: (i) To obtain spectra when there is a large transient absorption change by using a shifted excitation difference technique and (ii) to obtain high time resolution vibrational spectra of transient electronic states.

Controlled Assembly and Plasmonic Properties of Asymmetric Core–Satellite Nanoassemblies

The assembly of noble metal nanoparticles offers an appealing means to control and enhance the plasmonic properties of nanostructures. However, making nanoassemblies with easily modifiable gap distances with high efficiency has been challenging. Here, we report a novel strategy to assemble gold nanoparticles (AuNPs) into Janus-type asymmetric core-satellite nanostructures. Markedly different desorption efficiency between large and small AuNPs in ethanol allows us to prepare the asymmetric core-satellite nanoassemblies in a dispersed colloidal state with near 100% purity. The resulting nanoassemblies have well-defined structures in which a core AuNP (51 nm) is covered by an average of 13 ± 3 satellite AuNPs (13 nm) with part of the core surfaces left unoccupied. Strong surface plasmon coupling is observed from these nanoassemblies as a result of the close proximity between the core and the satellites, which appears significantly red-shifted from the surface plasmon resonance frequencies of the constituting nanoparticles. The dependence of the surface plasmon coupling on a gap distance of less than 3 nm is systematically investigated by varying the length of the alkanedithiol linkers. The asymmetric core-satellite nanoassemblies also serve as an excellent surface-enhanced Raman scattering substrate with an enhancement factor of ~10(6). Finally, we demonstrate that the presented assembly method is extendible to the preparation of compositionally heterogeneous core-satellite nanoassemblies.

Probing Quantum Plasmon Coupling Using Gold Nanoparticle Dimers with Tunable Interparticle Distances Down to the Subnanometer Range

The assembly of noble metal nanoparticles is an appealing means to control the plasmonic properties of nanostructures. Dimers are particularly interesting because they are a model system that can provide fundamental insights into the interactions between nanoparticles in close proximity. Here, we report a highly efficient and facile assembly method for dimers and other forms of assemblies. Gold nanoparticles (AuNPs) adsorbed on aminosilanized glass surfaces protect the silanes underneath the nanoparticles from hydrolysis. This masked desilanization allows us to prepare AuNP homodimers on glass slides with remarkably high yield (∼90%). The interparticle distance and, accordingly, the surface plasmon coupling are readily tuned at the molecular level using self-assembled monolayers of alkanedithiols. As the interparticle distance is reduced, the resonance surface plasmon coupling progressively redshifts, following the classical electromagnetic model. When the interparticle distance enters the subnanometer regime, however, the resonance band begins to blueshift and significantly broadens. The comparison of our observations with theoretical studies reveals that quantum tunneling effects play a significant role in the plasmonic response of AuNP dimers in the subnanometer gap region. The assembly method based on the masked desilanization is extendable to the formation of various other forms of nanoassemblies and, thus, will further our understanding of plasmonic interactions in nanoassemblies.

Direct observation of the ultrafast intersystem crossing in tris(2,2′-bipyridine)ruthenium(II) using femtosecond stimulated Raman spectroscopy

Time-resolved femtosecond stimulated Raman spectroscopy (FSRS) is used to explore the ultrafast intersystem crossing between the metal-to-ligand charge-transfer (MLCT) states of tris(2,2′-bipyridine)ruthenium(II) ( ). Excitation at 480 nm by a ∼35 fs actinic pump pulse initiates electron transfer from the metal to the bipyridine ligands and the subsequent changes in the vibrational structure of the ligands are probed by FSRS with high spectral (10 cm−1) and temporal (70 fs) resolution. The unique Raman spectral features of the 3MLCT state of appear with rise times from 100 to 130 fs. An upper limit for the initial 1MLCT state lifetime of <30 fs is determined by analysis of the spontaneous emission spectra and quantum yield. The ultrashort lifetime of the 1MLCT state is attributed to fast Franck–Condon vibrational and solvent relaxation of the excited singlet state into near degeneracy with the triplet state, leading to fast and efficient intersystem crossing.

Time-dependent and symmetry-selective charge-transfer contribution to SERS in gold nanoparticle aggregates.

We report the time- and symmetry-dependent surface-enhanced Raman scattering (SERS) of gold nanoparticle (AuNP) aggregates. The addition of p-aminothiophenol (p-ATP) instantly induces the aggregation of AuNPs, confirmed by large absorption in the near-IR region. Dynamic light scattering measurements show that the addition of p-ATP immediately assembles the AuNPs (13 nm) to form aggregates with a mean diameter of approximately 200 nm, which then further grow to a size of approximately 300 nm. Raman spectra acquired via time lapse show that the a(1)-symmetry bands of p-ATP are enhanced simultaneously with the formation of the aggregates, indicating that the electromagnetic enhancement largely contributes to the SERS of the AuNP aggregates. In contrast, the enhancement of the b(2)-symmetry bands occurs approximately 10 h after the formation of the aggregates and slowly progresses. The enhancement of the b(2) mode is attributed to the charge transfer between AuNPs and adsorbates, rather than the reorientation of the adsorbates because thiophenol and p-methylthiophenol that have surface structures and intermolecular interactions similar to those of p-ATP do not exhibit a symmetry-specific Raman enhancement pattern. To elucidate the disparity in the timescale between the charge-transfer resonance and the formation of the aggregates, we propose two models. A further close approach of the AuNPs constituting the aggregates causes the additional adsorption of the initially adsorbed p-ATP onto neighboring AuNPs, tuning the charge transfer state to be in resonance with the Raman excitation laser. Density functional theory calculations confirm the resonance charge-transfer tunneling through the bridging p-ATP in the AuNP-p-ATP-AuNP structures. Alternatively, the gradual continuing adsorption of p-ATP increases the local Fermi level of AuNPs into the region of resonant charge transfer from the Fermi level to the LUMO of the adsorbates. This model is corroborated by the faster appearance of b(2)-mode enhancement for the AuNPs with initially higher zeta potentials.

Dependence of line shapes in femtosecond broadband stimulated Raman spectroscopy on pump-probe time delay

The effect of the time delay between the picosecond Raman pump and the femtosecond Stokes probe pulse on the Raman gain line shape in femtosecond broadband stimulated Raman spectroscopy (FSRS) is presented. Experimental data are obtained for cyclohexane to investigate the dependence of the FSRS line shape on this time delay. Theoretical simulations of the line shapes as a function of the time delay using the coupled wave theory agree well with experimental data, recovering broad line shapes at positive time delays and narrower bands with small Raman loss side wings at negative time delays. The analysis yields the lower bounds of the vibrational dephasing times of 2.0 ps and 0.65 ps for the 802 and 1027 cm(-1) modes for cyclohexane, respectively. The theoretical description and simulation using the coupled wave theory are also consistent with the observed Raman gain intensity profile over time delay, reaching the maximum at a slightly negative time delay (approximately -1 ps), and show that the coupled wave theory is a good model for describing FSRS.

Surface Plasmon Coupling of Compositionally Heterogeneous Core–Satellite Nanoassemblies

Understanding plasmon coupling between compositionally heterogeneous nanoparticles in close proximity is intriguing and fundamentally important because of the energy mismatch between the localized surface plasmons of the associated nanoparticles and interactions beyond classical electrodynamics. In this Letter, we explore surface plasmon coupling between silver nanoparticles (AgNPs) and gold nanoparticles (AuNPs), assembled in the form of core-satellite structures. A recently developed assembly method allows us to prepare ultrapure core-satellite nanoassemblies in solution, where 50 nm AgNPs are surrounded by 13 nm AuNPs via alkanedithiol linkers. We observe changes in the plasmon coupling between the AgNP core and AuNP satellites as the core-to-satellite gap distance varies from 2.3 to 0.7 nm. Comparison with theoretical studies reveals that the traditional hybridized plasmon modes are abruptly replaced by charge-transfer plasmons at a ∼1 nm gap. Changes with the number of satellites are also discussed.

Bridging the Nanogap with Light: Continuous Tuning of Plasmon Coupling between Gold Nanoparticles

The control of nanogaps lies at the heart of plasmonics for nanoassemblies. The plasmon coupling sensitively depends on the size and the shape of the nanogaps between nanoparticles, permitting fine-tuning of the resonance wavelength and near-field enhancement at the gap. Previously reported methods of molecular or lithographic control of the gap distance are limited to producing discrete values and encounter difficulty in achieving subnanometer gap distances. For these reasons, the study of the plasmon coupling for varying degrees of interaction remains a challenge. Here, we report that by using light, the interparticle distance for gold nanoparticle (AuNP) dimers can be continuously tuned from a few nanometers to negative values (i.e., merged particles). Accordingly, the plasmon coupling between the AuNPs transitions from the classical electromagnetic regime to the contact regime via the nonlocal and quantum regimes in the subnanometer gap region. We find that photooxidative desorption of alkanedithiol linkers induced by UV irradiation causes the two AuNPs in a dimer to approach each other and eventually merge. Light-driven control of the interparticle distance offers a novel means of exploring the fundamental nature of plasmon coupling as well as the possibility of fabricating nanoassemblies with any desired gap distance in a spatially controlled manner.

Probing interfacial interactions using core-satellite plasmon rulers.

Understanding molecular interactions at the interfaces of nanoparticles is fundamentally important because they determine the stability, affinity, functionality, and assembly of nanoparticles. However, probing the governing intermolecular forces at the interfaces, particularly for the nanoparticles dispersed in solution, remains challenging. Here, we demonstrate that the interfacial interactions between citrate-capped gold nanoparticles and various molecular functional groups can be probed using a plasmon ruler, based on a well-defined core-satellite nanoassembly structure. Different nature of the interactions causes a subtle change in the interparticle distance, and the change is sensitively measured as a shift in the plasmon coupling band of the core-satellite nanoassemblies. Molecular interactions including covalent bonding, hydrogen bonding, electrostatic interactions, and van der Waals interactions are explored.