Theory of fluorescence and Raman scattering near resonance

Using a simple model for a molecular system in a bath, the cross section for Raman scattering around resonance is calculated. Without introducing constant relaxation times at the outset, the calculation yields a sharp coherent term, and a broad “hot” luminescence term. The second term is due to dephasing; its relative strength depends on the incident light frequency, and it disappears away from resonance.     

Transition polarizability model of induced resonance Raman optical activity

Induced resonance Raman optical activity (IRROA) proved to be a very sensitive method to detect molecular chirality. It is exhibited, for example, by complexes of lanthanides with chiral alcohols or ketones. So far, the phenomenon has not been understood at a quantitative level. To elucidate its mechanisms and to correctly relate the spectra to the structure, a transition polarizability model (TPM) is developed and applied to a camphor‐europium complex. The model well reproduces the high ROA/Raman intensity ratio of the IRROA observed experimentally. The results additionally indicate a fundamental role of the nonchiral fod ligand in the Eu(fod)₃ compound for the chirality enhancement. The TPM model thus serves as a guidance for both experimental and theoretical studies to come. © 2013 Wiley Periodicals, Inc.     

Polarization dispersion in resonance Raman scattering

A simple model for resonance Raman scattering by asymmetric and undisplaced symmetric vibrational modes is proposed. The model permits a detailed calculation of the polarization dispersion and the excitation spectrum in the region of the 0-0 and the 0-1 band of the resonating excited electronic state. It is directly amenable to experimental verification and shows good qualitative agreement with the experimental results available to date.     

A finite field method for calculating molecular polarizability tensors for arbitrary multipole rank

A finite field method for calculating spherical tensor molecular polarizability tensors α_lm;l′m′ = ?Δ_lm/??_l′m′* by numerical derivatives of induced molecular multipole Δ_lm with respect to gradients of electrostatic potential ?_l′m′* is described for arbitrary multipole ranks l and l′. Interconversion formulae for transforming multipole moments and polarizability tensors between spherical and traceless Cartesian tensor conventions are derived. As an example, molecular polarizability tensors up to the hexadecapole–hexadecapole level are calculated for water using the following ab initio methods: Hartree–Fock (HF), Becke three‐parameter Lee‐Yang‐Parr exchange‐correlation functional (B3LYP), Møller–Plesset perturbation theory up to second order (MP2), and Coupled Cluster theory with single and double excitations (CCSD). In addition, intermolecular electrostatic and polarization energies calculated by molecular multipoles and polarizability tensors are compared with ab initio reference values calculated by the Reduced Variation Space method for several randomly oriented small molecule dimers separated by a large distance. It is discussed how higher order molecular polarizability tensors can be used as a tool for testing and developing new polarization models for future force fields. © 2011 Wiley Periodicals, Inc. J Comput Chem, 2011     

Overtone intensities in resonance Raman scattering

A model calculation of resonance Raman scattering tensors has been carried out for a diatomic molecule with a harmonic potential for the ground state and a linear repulsive potential for the excited state. Expressions for scattering tensors have been obtained by using a series of recurrence formulas induced from the Green function of the nuclear hamiltonian of the repulsive potential of the excited state and nuclear wavefunctions for the harmonic potential. The relative scattering intensities of overtones depend on the gradient of the repulsive potential curve and are interpreted in terms of the overlap integrals between nuclear wavefunctions of upper and lower states.     

Stimulated Raman laser excitation of spontaneous resonance Raman scattering

The efficient conversion of the second and third harmonics of a Nd YAG laser to near UV radiation in the 395–500 nm range by stimulated Stokes (and anti-Stokes) Raman scattering (SRS) in a 1 m Raman oscillator containing compressed H₂ or D₂ is used as an excitation source for spontaneous resonance Raman spectroscopy (RRS). SRS excited RR spectra are shown for the anion radical of tetracyanoquinodimethane (TCNQ).     

Dipole polarizability derivatives calculated by the Kirkwood method

Derivatives, with respect to the symmetry coordinates, of the components of the dipole polarizabilities of HF, H₂O, and CH₄ are calculated using the Kirkwood method and a generalization of that method. The results for the bond-stretching derivatives are in reasonable agreement with those found by finite field calculations; those for angle changes are of the correct sign, but their magnitudes are in poor agreement with the finite field ones. The results are also analyzed using a four-parameter bond polarizability model.     

Silver-particle-based surface-enhanced resonance Raman scattering spectroscopy for biomolecular sensing and recognition

We demonstrate in this work that 2-μm-sized Ag (μAg) powders can be used as a core material for constructing biomolecular sensing/recognition units operating via surface-enhanced resonance Raman scattering (SERRS). This is possible because μAg powders are very efficient substrates for both the diffuse reflectance IR and the surface-enhanced Raman scattering–SERRS spectroscopic characterization of molecular adsorbates prepared in a similar manner on silver surfaces. Besides, the agglomeration of μAg particles in a buffer solution can be prevented by the layer-by-layer deposition of cationic and anionic polyelectrolytes such as poly(allylamine hydrochloride) (PAH) and poly(acrylic acid) (PAA). In this particular study, we used rhodamine B isothiocyanate (RhBITC) as a SERRS marker molecule, and μAg powders adsorbed consecutively with RhBITC and PAH–PAA bilayers were finally derivatized with biotinylated poly(l-lysine). On the basis of the nature of the SERRS peaks of RhBITC, those μAg powders were confirmed to selectively recognize streptavidin molecules down to concentrations of 10⁻¹⁰ g mL⁻¹. Since a number of different molecules can be used as SERS–SERRS marker molecules, the present method proves to be an invaluable tool for multiplex biomolecular sensing/recognition via SERS and SERRS.     

Surface enhanced resonance Raman scattering detection by fluorimeter

A commercially available fluorimeter with a white light source is used to detect surface enhanced resonance Raman scattering (SERRS). This approach allows facile tunability of the excitation source for SERRS.     

The local field effects in resonance Raman scattering Structural anisotropy studies in some nematic cyanophenyl derivatives

Different methods for the determination of the local field anisotropy in liquid crystals are analysed and the problems resulting from their application are outlined. One such method, namely that based on the comparison of the polarization of resonance Raman scattering and absorption bands is studied in more detail. The method is applied to determine the structural anisotropy for the 4-n-pentyl-(4'-cyanophenyl) derivatives of benzene, cyclohexane and bicyclooctane. To account for the difference between the optical properties of the probe and of the solvent at the wavelength of the scattered light the local field factor is treated theoretically within the framework of an anisotropic continuous dielectric medium.     

Non-adiabatic interaction and the resonance Raman scattering for a non-totally symmetric mode

It is shown that the inclusion of the non-adiabatic interaction between two electronic states distorts the mirror symmetry of the excitation spectrum and depolarization dispersion for resonance Raman scattering in the region of the 00 and the 01 band of the resonating excited electronic state.     

The local field effects in resonance Raman scattering Structural anisotropy studies in some nematic cyanophenyl derivatives

Abstract

Different methods for the determination of the local field anisotropy in liquid crystals are analysed and the problems resulting from their application are outlined. One such method, namely that based on the comparison of the polarization of resonance Raman scattering and absorption bands is studied in more detail. The method is applied to determine the structural anisotropy for the 4-n-pentyl-(4′-cyanophenyl) derivatives of benzene, cyclohexane and bicyclooctane. To account for the difference between the optical properties of the probe and of the solvent at the wavelength of the scattered light the local field factor is treated theoretically within the framework of an anisotropic continuous dielectric medium.     

Ligand polarizability contributions to the electronic Raman scattering in lanthanide(III) systems

A dynamic coupling mechanism for electronic Raman scattering in lanthanide(III) systems is investigated. Its ability to substantiate the small asymmetry in electronic Raman spectra reported recently is discussed. The importance of ligand anisotropy is stressed and selection rules for the dynamic coupling mechanism are derived.     

Identification and characterization of active and inactive species for surface-enhanced resonance Raman scattering

The surface-enhanced resonance Raman scattering (SERRS) activity of a statistically significant number of silver nanoparticles has been studied using a correlated SERRS mapping and transmission electron microscopy (TEM) method. TEM allowed the nature of each entity to be directly identified, and the SERRS activity was obtained from the corresponding SERRS map. Particles in various states of aggregation were analyzed to establish relative activities. It was established that SERRS activity is dependent on the specific batch of colloid tested. By averaging different colloid batches, it was shown that increasing SERRS activity is observed with increasing numbers of particles in the aggregates. By reducing the surface coverage of the particles to the extent that single moieties could be examined optically, the ratio of the relative activities of single particles, dimers, trimers, and larger aggregates was estimated. High-resolution TEM images of a number of active and inactive particles are reported. However, no clear correlation between microstructure and SERRS activity was observed.     

Biosensing using silver nanoparticles and surface enhanced resonance Raman scattering

Silver nanoparticles can be used to provide excellent surface enhanced resonance Raman scattering. Control of the surface chemistry and the use of appropriate protocols enables effective sensing of biomolecules.     

Direct method of calculating the dynamic scattering spectrum

A method of obtaining the scattering spectrum that bypasses the need to solve for the configurational distribution function of the macromolecules is presented. It involves the direct calculation of averages that appear in the structure factor expression. Application of the method to Rouse coils recovers Pecora's classical results. The method is applied to obtain the coherent spectrum of a solution of “encapsulated” dumbbells for which the configurational distribution is not available.     

Raman scattering in crystalline oligothiophenes: a comparison between density functional theory and bond polarizability model

Raman intensity of intramolecular and lattice modes of crystalline alpha-bithiophene (alpha-2T) are investigated within density functional theory using a nonlinear response formalism. First, comparison between the calculated Raman spectrum and the experimental data allows the assignment of the main Raman lines over the whole frequency range. Then, a bond polarizability (BP) model, limited to first neighbors, is built. We show that, although the BP model cannot reproduce the changes of dielectric susceptibility under individual atomic displacements, it is accurate enough to reproduce the profile of the unpolarized nonresonant Raman spectrum of alpha-2T powder. Finally, the BP model, fitted on our first-principles results on alpha-2T, is applied with success to the alpha-quaterthiophene polymorph phases and alpha-sexithiophene, demonstrating on practical examples that first-principles and BP approaches are powerful complementary tools to calculate the nonresonant Raman spectrum of alpha-2T and make reasonable predictions on larger oligothiophenes.     

Possibility of detecting oscillations in near resonance Raman scattering

Conditions are examined for detecting near resonant Raman oscillations, Gaussian pulses - commonly available in the laboratory - are shown to be unsuitable for such experiments; however, gaussian pulses with cut-off may create strong oscillations. The effects of fluctuations of the laser field and the effect of inhomogeneous broadening on the oscillations are studied.