Surface-Enhanced Hyper-Raman Spectroscopy

Abstract

Hyper-Raman scattering (HRS), first theoretically predicted by Decius and Rauch in 1959 [l] and experimentally demonstrated by Terhune et al. in 1965 [2], is a nonlinear optical process involving two incident photons (ω₀) and one emitted photon (ω). The emitted hyper- Raman photon frequencies are Raman-shifted relative to the second harmonic frequency (2ω₀) of the incident laser radiation [3–6]. The energy difference (2ω₀ – w) corresponds to one of the characteristicvibrational frequencies of the scattering medium or molecule. In Fig. 1 is given a schematic illustration of resonant and nonresonant HRS. The primary advantage of this nonlinear optical technique lies in its more relaxed selection rules compared with IR and Raman [7,8]. AlllR-active vibrational modes are hyper-Raman allowed, and those modes inactive in both IR and Raman (i.e., the “silent” modes) may be active in hyper-Raman scattering.     

Restoration of selection rules in nonadiabatic resonant inelastic x-ray scattering

Recently a new effect in the Raman scattering of x-ray radiation has been predicted theoretically and discovered in experiments, the effect of restoration of the selection rules for the scattering tensor under strong electron-vibrational interaction. We propose a fairly simple model for describing this effect, a model that allows for an exact solution and takes into account the real vibrational structure of the molecule and electron-vibrational interaction. Zh. éksp. Teor. Fiz. 112, 37–49 (July 1997)     

Molecular Force Field of Methanol

Abstract

Normal coordinate analysis was carried out on the vapor phase Raman and i.r. spectral data of methanol and its deuterated species to determine a vibrational force field. Based on the results of calculations, the 25-parameter molecular force field was analyzed and compared with the earlier studies and the vibrational band assignments were discussed in terms of the vibrational mode mixings, particularly, in the wavenumber region below 1500 cm^?1.     

Corrections to the Raman fundamental band of N2 and O2 due to molecular non-rigidity: computations and experiment

ABSTRACT

We present new, highly accurate, measurements of the fundamental band of the roto-vibrational Raman spectrum of molecular nitrogen and oxygen. Experimentally obtained spectra were used as a basis to derive information about the anisotropy of the polarisability tensor, including its dependence on rotational state due to molecular non-rigidity. Third-order perturbative calculations were used to determine corrections to the Raman scattering cross sections as a function of the rotational quantum numbers. Our results for the ratio of polarisability anisotropy at equilibrium divided by its first derivative for nitrogen are in agreement with values reported previously and are significantly different from historical data obtained for oxygen.     

Vibrational Band Intensities of Hydrocarbons

Abstract

The experimental observables of a vibrational spectrum are depicted either in the form of their positions, i.e., frequency relating the energy required in a given quantum transition, or as the intensities of absorption and scattering related to their transition probabilities. Expressed in terms of molecular parameters, the frequencies depend on the geometry, atomic masses, and intramolecular forces [11 while the band intensities [2] reflect changes in dipole moment (infrared) or polarizabilities (Raman) which are caused during a vibrational displacement and are related to movement of electronic charges within the individual bonds. The mathematical basis for determining vibrational frequencies was well established as early as 1940 by Wilson [3] and others [4, 51. Applying the interpretation of vibrational spectra has become routine in the multitudinous disciplines of chemical literature [6–26]. Accounts of infrared and Raman spectra [27–29], collection of literature [30], and reasonable sets of intramolecular forces [31, 321 are now available for the prediction of normal frequencies of hydrocarbons.     

Characteristics of multiple-photon dissociation of OsO4 molecule by two frequency tunable CO2-laser pulses

Using two-frequency technique for the multiple photon dissociation of OsO₄ molecule by IR laser radiation, the following new results have been obtained: 1. the narrow resonances of multiple photon absorption on few low lying vibrational transitions have been found in the dissociation yield as a function of exciting frequency ν₁; 2. the structure of the dissociation yield as a function of dissociating frequency ν₂ connected with high lying vibrational transition has been studied; 3. the kinetic of the vibration relaxation of high vibrationally excited molecules was investigated; 4. the unimolecular character of the multiple photon dissociation of OsO₄ has been proved.     

Charge transfer effects in surface enhanced Raman scattering

Surface enhanced Raman scattering (SERS) due to charge transfer interactions between the adsorbed molecule and the metal surface is analyzed using the semiempirical Wolfsberg-Helmholz method¹ to relate the molecule-surface interactions and the resulting charge transfer states to the overlap integrals between the metal conduction-band orbitals and an acceptor or donor molecular orbital of the molecule. Calculations for the model system of ethylene adsorbed on silver (approximated as a simple cubic metal with tight binding wave functions constructed from Ag 5s valence orbitals), with charge-transfer excitation of an electron from the metal to the antibonding ethylene π orbital, show that charge-transfer Raman enhancements of the order of 10 to 1000 are possible if the charge-transfer band is partially resonant with the exciting radiation. The net enhancement is the product of the charge-transfer gain and the electrodynamic enhancement due to plasmon resonances at surface roughness elements. Symmetric vibrations usually will be enhanced substantially more than nonsymmetric ones by charge-transfer because, in contrast to non-resonant Raman scattering, the vibrational coupling is primarily Franck- Condon (due to differences in the equilibrium nuclear configurations of the ground and excited charge transfer states and the resulting nonorthogonality of different vibrational sublevels of these states) rather than Herzberg-Teller (due to vibrationally induced changes in the electronic wave functions). The charge-transfer mechanism is selective with the most enhanced vibrations involving those atoms which experience the greatest change in electron density between the ground and excited charge-transfer state. A recent report of SERS for benzene on platinum,² strongly suggests charge-transfer enhancement because the electromagnetic-field-enhancing plasmon resonances are strongly damped in this metal.The complete paper will be published in the December 1, 1982 issue of the Journal of Chemical Physics.     

Vibrational Spectra of 4-Benzoylpiridine and the 18O Substituted Derivative

Abstract

Infrared and Raman spectra of 4-benzoylpiridine (4BP) and its ¹⁸O substituted derivative have been recorded in the solid and in the molten state. Polarized Raman spectra in the molten state have also been measured. The assignment of the vibrational bands is performed on the basis of isotopic shifts, group vibrational concept and polarization features of the normal modes. The previous assignment of the in- and out-of-plane deformations of the carbonyl group and the fundamentals below 700 cm^?1 are questioned and corrected.     

Raman spectroscopy and polarization: Selected case studies

We show, through several selected case studies, the potential benefits that can be obtained by controlling the polarization states of the exciting and scattered radiations in a Raman scattering experiment. When coupled with polarization control, Raman spectroscopy is thus capable of providing extra information on the structural properties of the materials under investigation. The experimental examples presented in this work are taken from the area of both conventional, i.e., far-field, as well as from near-field Raman spectroscopy. They cover topics such as the stress tensor measurement in strained semiconductor structures, the vibration mode assignment in pentacene thin films and the Raman scattering tensor determination from near-field measurements on azobenzene monolayers. The basic theory necessary for modelling the far- and near-field polarized Raman responses is also given and the model efficiency is illustrated on the experimental data.     

First experiments on field photodesorption IR spectroscopy

The ion current of adsorbed water molecules is studied experimentally as a function of the frequency of near-IR radiation incident on a surface at frequencies in the intrinsic vibrational bands of the water molecule. The ions are produced by nonequilibrium field surface ionization. The observed band (near one of the combination frequencies) has a width of 100 cm⁻¹ and is shifted relative to the free molecular band by 130 cm⁻¹. Estimates show that the cross section for absorption of the radiation by the adsorbed molecules is 3–4 orders of magnitude larger than for free molecules, as is typical of surface processes. Zh. Tekh. Fiz. 69, 123–127 (September 1999)     

Nonlinear interferometric vibrational imaging

Coherent anti-Stokes Raman scattering (CARS) processes are "coherent," but the phase of the anti-Stokes radiation is lost by most incoherent spectroscopic CARS measurements. We propose a Raman microscopy imaging method called nonlinear interferometric vibrational imaging, which measures Raman spectra by obtaining the temporal anti-Stokes signal through nonlinear interferometry. With a more complete knowledge of the anti-Stokes signal, we show through simulations that a high-resolution Raman spectrum can be obtained of a molecule in a single pulse using broad band radiation. This could be useful for identifying the three-dimensional spatial distribution of molecular species in tissue.     

On the mechanism responsible of Raman enhancement on carbon allotropes surfaces: the role of molecule‐surface vibrational coupling in SERS

The ability of different carbon allotropes surfaces as potential substrates for enhanced Raman spectroscopy is analysed theoretically and the factors responsible of the Raman‐enhancing mechanism deeply scrutinised. Our analysis is based on the partition of the Raman tensor into molecule and surface terms, which leads to three different contributions to the Raman activity (‘molecule’, ‘surface’ and ‘intermolecular’). Both static and pre‐ resonance conditions are considered in our analysis of the Raman spectra of pyridine adsorbed on model planar and curved surfaces and the three contributions to the Raman activity obtained separately. At static conditions, there is a general decrease in the Raman activity of vibrational modes associated to the molecule, proportional to the strength of the molecule–surface interaction. This stems from a reduction of the polarizability of pyridine upon its adsorption on the carbon surface. Under pre‐resonance conditions, the surface contributes significantly to the Raman activity of the pyridine vibrational modes, even if the electronic transition involves exclusively energy levels from the surface. This is because of small vibrational couplings between molecular and surface modes which are negligible in metallic surface‐like silver. It suggests also the possibility of finding similar effects in metallic surface built from lighter atoms like silicon or aluminium. Copyright © 2015 John Wiley & Sons, Ltd.     

Hot luminescence in polyacetylene

We propose that the unusual frequency dependent lineshapes observed in Raman scattering experiments on polyacetylene are due to hot luminescence in very long polyene chains. Employing a generalized equation of motion technique we find that a photoexcited polyene is unstable with respect to a variety of symmetry lowering distortions which vary as a function of the frequency of the exciting radiation. Radiative decay during this relaxation is observably strong in the inelastically scattered photon spectrum and would explain the dominant observed lineshape variations.     

Raman tensor analysis of hexagonal polyoxymethylene and its application to study the molecular arrangement in highly crystalline electrospun nanofibers

The orientation dependence in space of Raman‐active vibrations in the hexagonal structure of polyoxymethylene (POM) is discussed in terms of Raman tensor elements as intrinsic physical parameters of the lattice. The variation of polarized intensity for the A₁ and the E₁ vibrational modes with respect to the POM molecular orientation is systematically studied, from both theoretical and experimental viewpoints, according to the symmetry assignments of each vibrational mode. A set of working equations including the Raman selection rules associated with the A₁ and the E₁ modes and the orientation distribution function are explicitly formulated and validated by means of a least‐square fitting procedure on experimental data. In addition, an approach based on the introduction of orientation distribution functions is applied to quantitatively assess and compare on a statistical base the molecular orientation of two different types of electrospun POM nanofibers. Copyright © 2012 John Wiley & Sons, Ltd.     

Electronic and Resonance Raman Spectra of a Multibridged Iron Porphyrin

Abstract

Reported are the electronic and resonance Raman (rR) spectra of a multibridged iron porphyrin derived from meso-tetra(4-pyridil)porphynate iron(II) by complexing the pyridine residues with [Ru^II(edta)]^2- ions. The polymetallated system exhibits the characteristic Soret band at 428 nm (log ε = 5.2) and a shoulder around 465 nm (4.6). The rR enhancement of the porphyrin vibrational modes is similar to those previously reported for typical porphyrins; however, an additional feature appears around 465 nm, associated with the selective enhancement of some pyridine vibrational modes. Based on the rR excitation profiles the absorption band at 465 nm was assigned to a Ru^II-to-pyridine dπ→Pπ? charge-transfer transition.     

Raman echo under medium excitation by extremely short pulses

A generalization of the Bloembergen-Shen model to Raman active molecules with an arbitrary number of normal modes was suggested. The generalized model was used to study Raman echo signal characteristics when a system of molecules was excited by pulses of widths up to one period of optical oscillations. It was shown that a large number of echo responses on Stokes and anti-Stokes components could arise even under a two-pulse action in a continuous monochromatic pumping field. The number of echo responses depended on the number of molecular normal modes and the geometry of measurements. At small exciting pulse “areas,” the echo responses whose Stokes and anti-Stokes components corresponded to normal vibrational modes of a molecule had the highest intensity, whereas the components formed by normal mode combinations were strongly suppressed.     

Rotational-vibrational polarizability operator for nonlinear X<Subscript>2</Subscript>Y molecules: Application to the calculation of the Raman spectrum of the H<Subscript>2</Subscript>O molecule

For nonlinear X₂Y molecules, an expression for the transformed polarizability operator is obtained with an accuracy of up to the second order of the theory of perturbation. This operator is applied to the calculation of the intensities of Raman lines of the H₂O molecule. The corrections to the polarizability of the molecule associated with the vibrational-rotational interaction are shown to considerably change the integral intensity of a pure rotational band. The dependence of the average polarizability of the molecule on the vibrational quantum number V ₂, describing deformation vibrations, is estimated.     

Vibrational spectra of a GaS single crystal

The Raman and infrared active long wavelength phonons of a GaS single crystal were studied at different temperatures in the 10–600 cm^?1 range. Properly polarized Raman spectra could be obtained with the 4880 Å exciting line and the previous assignment of the E_1g modes controversed recently could be confirmed. Infrared spectra were recorded in the 30–600 cm^?1 region. The vibrational frequencies of the crystal were also calculated using a method developed by Wieting and six new frequencies corresponding to infrared and Raman inactive modes have been proposed.We have observed that the degree of leakage of scattered intensity in unallowed polarizations increases when the wavelength of the exciting line moves off the exciton absorption front. The phonon at 74 cm^?1 was particularly sensitive and the question of the antiresonant behaviour of this compound is raised.     

Vibrational spectroscopic studies of the structure of di‐amino acid peptides. Part II: cyclo(L‐Asp‐L‐Asp) in the solid state and in aqueous solution

Solid‐state protonated and N,O‐deuterated Fourier transform infrared (IR) and Raman scattering spectra together with the protonated and deuterated Raman spectra in aqueous solution of the cyclic di‐amino acid peptide cyclo(L ‐Asp‐L ‐Asp) are reported. Vibrational band assignments have been made on the basis of comparisons with previously cited literature values for diketopiperazine (DKP) derivatives and normal coordinate analyses for both the protonated and deuterated species based upon DFT calculations at the B3‐LYP/cc‐pVDZ level of the isolated molecule in the gas phase. The calculated minimum energy structure for cyclo(L ‐Asp‐L ‐Asp), assuming C₂ symmetry, predicts a boat conformation for the DKP ring with both the two L ‐aspartyl side chains being folded slightly above the ring. The CO stretching vibrations have been assigned for the side‐chain carboxylic acid group (e.g. at 1693 and 1670 cm⁻¹ in the Raman spectrum) and the cis amide I bands (e.g. at 1660 cm⁻¹ in the Raman spectrum). The presence of two bands for the carboxylic acid CO stretching modes in the solid‐state Raman spectrum can be accounted for by factor group splitting of the two nonequivalent molecules in a crystallographic unit cell. The cis amide II band is observed at 1489 cm⁻¹ in the solid‐state Raman spectrum, which is in agreement with results for cyclic di‐amino acid peptide molecules examined previously in the solid state, where the DKP ring adopts a boat conformation. Additionally, it also appears that as the molecular mass of the substituent on the C^α atom is increased, the amide II band wavenumber decreases to below 1500 cm⁻¹; this may be a consequence of increased strain on the DKP ring. The cis amide II Raman band is characterized by its relatively small deuterium shift (29 cm⁻¹), which indicates that this band has a smaller N H bending contribution than the trans amide II vibrational band observed for linear peptides. Copyright © 2009 John Wiley & Sons, Ltd.