Surface-enhanced hyper-Raman Scattering Spectra Research Articles

Surface-enhanced hyper-Raman scattering of Rhodamine 6G isotopologues: Assignment of lower vibrational frequencies.

We report a comprehensive experimental and theoretical study of the lower-wavenumber vibrational modes in the surface-enhanced hyper-Raman scattering (SEHRS) of Rhodamine 6G (R6G) and its isotopologue R6G-d4. Measurements acquired on-resonance with two different electronic states, S1 and S2, are compared to the time-dependent density functional theory computations of the resonance hyper-Raman spectra and electrodynamics-quantum mechanical computations of the SEHRS spectra on-resonance with S1 and S2. After accounting for surface orientation, we find excellent agreement between experiment and theory for both R6G and its isotopologue. We then present a detailed analysis of the complex vibronic coupling effects in R6G and the importance of surface orientation for characterizing the system. This combination of theory and experiment allows, for the first time, an unambiguous assignment of lower-wavenumber vibrational modes of R6G and its isotopologue R6G-d4.

Bio‐probing with nonresonant surface‐enhanced hyper‐Raman scattering excited at 1,550 nm

AbstractThe two‐photon excited process of surface‐enhanced hyper‐Raman scattering (SEHRS) provides advantages for studies of complex biological samples, yet suitable SEHRS nanoprobes and labels, as well as experimental conditions, must be established. Here, SEHRS spectra of the four reporter molecules (2‐naphthalenethiol [2‐NAT], para‐aminothiophenol (pATP), para‐nitrothiophenol (pNTP), and crystal violet), as well as the two antidepressant drugs (desipramine and imipramine) were obtained at an excitation wavelength of 1,550 nm using different citrate‐stabilized gold nanoparticles and silver nanoparticles, and under conditions that permit experiments with living cultured cells. As the results suggest, the short‐wave infrared laser excitation and the hyper‐Raman scattered light (corresponding to wavelengths > 775 nm) match the plasmonic properties of the employed gold and silver nanoaggregates, as well as the requirements regarding the viability of the cells. The two‐photon excited spectra of three types of SEHRS labels containing 2‐NAT as reporter inside macrophage cells show that molecules in the cellular environment can also be observed. The possibility to use short‐wave infrared excitation with gold nanostructures has important implications for the utilization of SEHRS in bio‐probing.

Surface-Enhanced Hyper Raman Spectra of Aromatic Thiols on Gold and Silver Nanoparticles.

We report the two-photon excited nonresonant surface-enhanced hyper Raman scattering (SEHRS) spectra of six aromatic thiol molecules during their interaction with gold and silver nanostructures. SEHRS spectra were obtained from thiophenol, benzyl mercaptan, and phenylethyl mercaptan and from the three isomers 2-aminothiophenol (2-ATP), 3-aminothiophenol (3-ATP), and 4-aminothiophenol (4-ATP). All SEHRS spectra were excited off-resonance at a wavelength of 1064 nm and compared to surface-enhanced Raman scattering (SERS) spectra excited at 785 nm or at 633 nm. The SEHRS spectra show a different interaction of thiophenol, benzyl mercaptan, and phenylethyl mercaptan with silver and gold nanostructures. Density functional theory calculations were used to support band assignments, in particular, for the unknown SERS spectrum of 3-ATP, and identify a band of phenylethyl mercaptan as a vibrational mode unique to the SEHRS spectrum and very weak in the Raman and infrared spectra. 2-ATP, 3-ATP, and 4-ATP show a different interaction with gold nanostructures that was found to depend on pH. Bands in the SEHRS spectrum of 2-ATP could be assigned to 2,2′-dimercaptoazobenzene, suggested to be obtained in a plasmon-assisted reaction that occurred during the SEHRS experiment. The results provide the basis for a better characterization of organic thiols at surfaces in a variety of fields, including surface functionalization and plasmonic catalysis.

Non-Condon Effects in the Resonance Hyper-Raman Scattering of Chalcogen-Substituted Rhodamine Derivatives

Molecules with a strong two-photon response have gained significant interest because of their applications in two-photon imaging, all-optical switching, and energy up-conversion. The surface-enhanced hyper-Raman scattering (SEHRS) of tetramethyl chalcogenorosamines are taken on- and off-resonance and compared to time-dependent density functional theory calculations. Specifically, changes in the SEHRS spectra are tracked as a function of structural geometry because of perturbations induced by larger chalcogen atom substitutions to the xanthene ring. Here we show that the spectral changes and non-Condon effects can be understood by tracking the vibrational normal modes and the vibrationally induced changes to the highest occupied molecular orbitals. With a system in place to explore the relationship between structural geometry and nonlinear properties, various rhodamine derivatives can be characterized as a means to optimally design a series of two-photon bright compounds.

Utilizing Molecular Hyperpolarizability for Trace Analysis: A Surface-Enhanced Hyper-Raman Scattering Study of Uranyl Ion.

Surface-enhanced hyper-Raman scattering (SEHRS), the nonlinear analog of surface-enhanced Raman scattering (SERS), provides unique spectral signatures arising from the molecular hyperpolarizability. In this work, we explore the differences between SERS and SEHRS spectra obtained from surface-bound uranyl ion. Exploiting the distinctive SEHRS bands for trace detection of the uranyl ion, we obtain excellent sensitivity (limit of detection = 90 ppb) despite the extreme weakness of the hyper-Raman effect. We observe that binding the uranyl ion to the carboxylate group of 4-mercaptobenzoic acid (4-MBA) leads to significant changes in the SEHRS spectrum, whereas the surface-enhanced Raman scattering (SERS) spectrum of the same complex is little changed. The SERS and SEHRS spectra are also examined as a function of both substituent position, using 2-MBA, 3-MBA, and 4-MBA, and the carbon chain length, using 4-mercaptophenylacetic acid and 4-mercaptophenylpropionic acid. These results illustrate that the unique features of SEHRS can yield more information than SERS in certain cases and represent the first application of SEHRS for trace analysis of nonresonant molecules.

Specific Interaction of Tricyclic Antidepressants with Gold and Silver Nanostructures as Revealed by Combined One- and Two-Photon Vibrational Spectroscopy

We report two-photon excited nonresonant surface-enhanced hyper Raman scattering (SEHRS) spectra of tricyclic antidepressant (TCA) molecules during their interaction with biocompatible gold nanostructures and with silver nanostructures. The SEHRS spectra of amitriptyline, desipramine, and imipramine are compared with surface-enhanced Raman scattering (SERS) spectra on both kinds of nanoparticles, obtained with excitation at 532 and 785 nm. The SEHRS spectra of the TCA molecules show several intense contributions by infrared-active vibrations. Combining SEHRS with SERS therefore enables a comprehensive vibrational characterization of the interaction of the molecules with the nanostructures. SEHRS and SERS data indicate that the molecules interact with the silver nanostructures mainly via their ring moiety. In contrast, in the interaction with gold, the methylaminopropyl side chain plays a very important role, along with parts of the ring system. It is possible to obtain the spectra of the molecules with ne...

Manifestation of a strong quadrupole interaction and peculiarities in the SERS and SEHRS spectra of 4,4'-bipyridine

The paper analyzes Surface Enhanced Raman Scattering (SERS) and Surface Enhanced Hyper Raman Scattering (SEHRS) spectra of 4,4'-bypiridine molecule for two possible geometries, which are described by D2 and D2h symmetry groups. It is pointed out on appearance of sufficiently strong lines, caused by vibrations with the unit irreducible representation for both possible configurations. Appearance of these lines in the SEHRS spectrum points out the existence of a strong quadrupole light-molecule interaction. In addition one observes the lines, caused by vibrations both with the unit irreducible representations A or Ag and the irreducible representation B1 or B1u. The last ones describe transformational properties of the dz component of the dipole moment, which is perpendicular to the surface. This property of the spectrum is caused by peculiarity of the geometry of the molecule, which consists of two benzene rings, which are weakly connected with each other. The linear combinations of the vibrations of the rings create two nearly degenerated symmetric and anti symmetrical states, which cannot be identified in the experimental spectra. The result is in a full agreement with the dipole-quadrupole theory of SERS and SEHRS.

Surface-Enhanced Resonance Hyper-Raman Scattering Elucidates the Molecular Orientation of Rhodamine 6G on Silver Colloids.

Herein, we utilize surface-enhanced hyper-Raman scattering (SEHRS) under resonance conditions to probe the adsorbate geometry of rhodamine 6G (R6G) on silver colloids. Our results show resonance SEHRS is highly sensitive to molecular orientation due to non-Condon effects, which do not appear in its linear counterpart surface-enhanced Raman scattering. Comparisons between simulated and measured SEHRS spectra reveal R6G adsorbs mostly perpendicular to the nanoparticle surface along the ethylamine groups with the xanthene ring oriented edgewise. Our results expand upon previous studies that rely on indirect, qualitative probes of R6G's orientation on plasmonic substrates. More importantly, this work represents the first determination of adsorbate geometry by SEHRS and opens up the possibility to study the orientation of single molecules in complex, plasmonic environments.

Simulating Surface-Enhanced Hyper-Raman Scattering Using Atomistic Electrodynamics-Quantum Mechanical Models.

Surface-enhanced hyper-Raman scattering (SEHRS) is the two-photon analogue of surface-enhanced Raman scattering (SERS), which has proven to be a powerful tool to study molecular structures and surface enhancements. However, few theoretical approaches to SEHRS exist and most neglect the atomistic descriptions of the metal surface and molecular resonance effects. In this work, we present two atomistic electrodynamics-quantum mechanical models to simulate SEHRS. The first is the discrete interaction model/quantum mechanical (DIM/QM) model, which combines an atomistic electrodynamics model of the nanoparticle with a time-dependent density functional theory description of the molecule. The second model is a dressed-tensors method that describes the molecule as a point-dipole and point-quadrupole object interacting with the enhanced local field and field-gradients (FG) from the nanoparticle. In both of these models, the resonance effects are treated efficiently by means of damped quadratic response theory. Using these methods, we simulate SEHRS spectra for benzene and pyridine. Our results show that the FG effects in SEHRS play an important role in determining both the surface selection rules and the enhancements. We find that FG effects are more important in SEHRS than in SERS. We also show that the spectral features of small molecules can be accurately described by accounting for the interactions between the molecule and the local field and FG of the nanoparticle. However, at short distances between the metal and molecule, we find significant differences in the SEHRS enhancements predicted using the DIM/QM and the dressed-tensors methods.

Surface-Enhanced Hyper-Raman Spectra of Adenine, Guanine, Cytosine, Thymine, and Uracil.

Using picosecond excitation at 1064 nm, surface-enhanced hyper-Raman scattering (SEHRS) spectra of the nucleobases adenine, guanine, cytosine, thymine, and uracil with two different types of silver nanoparticles were obtained. Comparing the SEHRS spectra with SERS data from the identical samples excited at 532 nm and with known infrared spectra, the major bands in the spectra are assigned. Due to the different selection rules for the one- and two-photon excited Raman scattering, we observe strong variation in relative signal strengths of many molecular vibrations obtained in SEHRS and SERS spectra. The two-photon excited spectra of the nucleobases are found to be very sensitive with respect to molecule–nanoparticle interactions. Using both the SEHRS and SERS data, a comprehensive vibrational characterization of the interaction of nucleobases with silver nanostructures can be achieved.

Surface-Enhanced Raman and Surface-Enhanced Hyper-Raman Scattering of Thiol-Functionalized Carotene.

A thiol-modified carotene, 7′-apo-7′-(4-mercaptomethylphenyl)-β-carotene, was used to obtain nonresonant surface-enhanced Raman scattering (SERS) spectra of carotene at an excitation wavelength of 1064 nm, which were compared with resonant SERS spectra at an excitation wavelength of 532 nm. These spectra and surface-enhanced hyper-Raman scattering (SEHRS) spectra of the functionalized carotene were compared with the spectra of nonmodified β-carotene. Using SERS, normal Raman, and SEHRS spectra, all obtained for the resonant case, the interaction of the carotene molecules with silver nanoparticles, as well as the influence of the resonance enhancement and the SERS enhancement on the spectra, were investigated. The interaction with the silver surface occurs for both functionalized and nonfunctionalized β-carotene, but only the stronger functionalization-induced interaction enables the acquisition of nonresonant SERS spectra of β-carotene at low concentrations. The resonant SEHRS and SERS spectra are very similar. Nevertheless, the SEHRS spectra contain additional bands of infrared-active modes of carotene. Increased contributions from bands that experience low resonance enhancement point to a strong interaction between silver nanoparticles and electronic levels of the molecules, thereby giving rise to a decrease in the resonance enhancement in SERS and SEHRS.

Electrodynamical forbiddance of strong quadrupole light–molecule interaction and peculiarities of the SEHR spectra in the methane molecule

It is demonstrated that the strong quadrupole light–molecule interaction, which is responsible for the most enhancement of Surface Enhanced Hyper Raman Scattering (SEHRS), experiences so-called electrodynamical forbiddance in the methane molecule and molecules with cubic symmetry groups and does not influence on formation of the SEHRS spectra. This forbiddance results in the fact that the lines, caused by the totally symmetric vibrations, which are observed in pyrazine and phenazine, must be slight, or absent at all. In this case, in methane, the most enhanced lines are those, caused by vibrations, transforming after the irreducible representations T1, or T2.

Investigation of Linear and Nonlinear Raman Scattering for Isotopologues of Ru(bpy)32+

Tris(2,2′-bipyridine)ruthenium(II), Rubpy, an important transition metal complex for its robust photochemistry, is studied using simulated resonance Raman scattering (RRS) and resonance hyper-Raman scattering (RHRS) in comparison to measured surface-enhanced Raman scattering (SERS) and surface-enhanced hyper-Raman scattering (SEHRS). Detailed examination of the simulated data shows that many of the observed features in the experiments are captured by the theory. For the metal-to-ligand charge transfer (MLCT) absorption band at 452 nm, it is demonstrated that the shoulder on the absorption band at 425 nm is not a vibronic feature and that the line shape should be considered as coming from two separate MLCT states. We find that good agreement can be obtained by comparing simulated spectra to the SERS and SEHRS spectra on resonance with the absorption band. However, the simulations do not capture the high sensitivity of relative peak intensities observed during wavelength scanned SERS and SEHRS experiments. This result is interpreted on the basis of discussion of the literature and the approximations made in the vibronic model, where it is concluded that the simulations underestimate interference effects. These results demonstrate the complexity of using theoretical methods for accurately describing the electronic structure of large molecules, and that commonly used exchange-correlation functionals like B3LYP and LC-PBE cannot completely describe all of the vibronic features in the Raman scattering of Rubpy.

Strong quadrupole interaction of light with molecules and its manifestation in surface-enhanced hyper-Raman scattering spectra

The possibility of the giant enhancement of hyper-Raman scattering by molecules adsorbed on rough metal surfaces is demonstrated. The theory is based on the qualitative consideration of electromagnetic field enhancement near some model rough surfaces and individual irregularities, as well as on the quantum-mechanical features of dipole and quadrupole interactions of light with molecules (as in the theory of surface-enhanced Raman scattering), proposed by the author. A consideration of symmetric molecules makes it possible to obtain selection rules for surface-enhanced hyper-Raman scattering (SEHRS) spectra and establish such a regularity as the occurrence of strong forbidden lines (which are due to totally symmetric vibrations); these lines are transformed according to unitary irreducible representation in molecules with the symmetry groups Cnh, D, and higher. An analysis of the data in the literature for trans-1,2-bis (4-pyridyl)ethylene and pyridine molecules shows that their spectra can be explained in terms of the dipole-quadrupole theory of SEHRS. At the same time, the analysis of the SEHRS spectra of pyrazine revealed the presence of strong forbidden bands due to totally symmetric vibrations. This finding substantiated the proposed theory, which makes it possible to interpret the entire spectrum in detail. These results are in good agreement with the general mechanism of the optical effects enhanced by molecules adsorbed on metal surfaces, which was developed by the author.

Resonant and nonresonant surface-enhanced hyper-Raman spectroscopy with a picosecond laser. Effect of the excitation pulse width

We report resonant and nonresonant surface-enhanced hyper-Raman scattering (SEHRS) spectra of basic fuchsin and 3-hydroxykynurenine in the Ag colloid system with a picosecond pulse laser of high repetition rate (82 MHz). It is demonstrated that, at constant average power, fiber-optic compression of the 100 ps fundamental output of a Nd:YAG laser to ≈ 5 ps increases the intensities of surface-enhanced hyper-Raman scattering and second-harmonic generation by approximately one order of magnitude. We have thus obtained high-quality SEHRS spectra for both molecules with only 0.1 W laser excitation. These results are significant in the development of SEHRS as a useful spectroscopic technique.