Incident-angle dependence of the sensitivity of second-harmonic generation of an oxacyanine dye in an LB film.

The second-harmonic generation of a cyanine dye in an LB film was investigated by varying the incident angle of the excitation laser. There was a clear dependence on the incident angle, which was simulated by a simple model. Thus, a highly sensitive determination should be carried out at such an angle where the efficiency of the second-harmonic generation shows its maximum.     

Azo-azulene derivatives as second-order nonlinear optical chromophores

The molecular and solid state nonlinear optical (NLO) properties of several (phenylazo)-azulenes are investigated. In particular, (4-nitrophenylazo)-azulene (2b) exhibits a quadratic hyperpolarizability (beta(vec)) of 80 x 10(-30) cm5esu recorded at 1.907 microm by the electric field-induced second-harmonic (EFISH) technique. This molecular material, which crystallizes in the monoclinic noncentrosymmetric space group Pc, exhibits an efficiency 420 times that of urea in second-harmonic generation. The origin of the optical nonlinearity in azo-azulene is discussed in relation with crystal structures and semiempirical calculations within the INDO/SOS formalism, and compared with that of the well known disperse red one (DR1) organic dye.     

Roughness-induced acoustic second-harmonic generation during electrochemical metal deposition on the quartz-crystal microbalance

This paper reports on the relation between the surface roughness and emission of compressional waves from the surface of an electrochemical quartz-crystal microbalance. The detection of the compressional waves took place with an ultrasonic microphone and the quartz crystal itself. As a model process, the electrochemical deposition of copper from an acidic copper sulfate solution has been chosen. For this system, the roughness of the layer can be tuned via the current density. Roughness may be a source of the longitudinal waves at twice the frequency of the exciting shear wave (acoustic second-harmonic generation, ASHG) if the flow profile above the quartz-crystal surface is not entirely laminar. Slight deviations from the laminar flow can be reached at high amplitudes of oscillation. Comparing the ASHG efficiency of a rough and smooth surface, we find that the rough surface is more efficient in generating second-harmonic waves. This suggests that ASHG can be used to obtain a roughness parameter independent from the resonance frequency or bandwidth (damping) of a quartz-crystal resonator. Such an independent determination of roughness should be very interesting in practical applications.     

Sorption of uranyl cations on a rutile (001) single crystal monitored by surface second-harmonic generation

The rotational anisotropy of second-harmonic generation at the surface of a (001) single-crystal rutile is obtained in the presence of uranyl cations sorbed at the surface from acidic solutions at various concentrations. Surface second-harmonic generation appears to be sensitive to the presence of uranyl cations on the rutile samples. Evolution of the anisotropy pattern with initial uranyl concentration is analyzed through a phenomenological model. The elements obtained for the nonlinear susceptibility tensor Chi(2) for each sample significantly constrain the geometry of the possible sorption complexes between uranyl cations and rutile and lead to the proposition of two sorption sites involving different oxygen atoms of the rutile surface.     

Detection of protein conformational change by optical second-harmonic generation

An ability to detect and track conformational change in real time is essential to understanding the dynamic relationship between structure and function in biological molecules. Here I show that second-harmonic generation (SHG), a surface-selective technique, offers a new means to probe structural dynamics. A protein, calmodulin, was labeled with a second-harmonic-active dye and immobilized to a surface. Although neither the labeling nor the immobilization was done in a site-specific manner, an overall net orientation of the labels was produced relative to the surface plane. Conformational change of the protein induced by calcium alters the average tilt angle of the labels and causes a change in the intensity of second-harmonic radiation generated by the surface. As SHG is spatially and temporally coherent and depends quantitatively on the structural details of a surface, the method described here should serve as the starting point for more detailed studies of the mechanism of conformational change in molecules, as well as related topics such as protein folding. SHG's surface selectivity also suggests its use in a range of biological applications which require detection of surface-bound molecules.     

Adsorbate resonance enhancement in optical surface second-harmonic generation: S on Pd(100)

Optical second-harmonic generation from a fixed-frequency laser at λ = 1064 nm has been used to monitor the adsorption of sulfur atoms on a Pd(100) single-crystal surface. The signal observed was dominated by the contribution from the adsorbate atoms to the second-order susceptibility due to a resonance enhancement from a nearby electronic state of the S atom. This enhancement rendered an adsorbate sensitivity of 0.01 monolayer possible.     

Organic materials for non-linear optics nitropyridine derivatives

A variety of nitropyridine derivatives have been prepared and their second-harmonic generation (SHG) efficiencies measured in the powder form. Based on these powder measurements, two new compounds are the most non-linear substances known with absorption edge cutoffs less than 0.45 μm.     

Terbium luminescence sensitized through three-photon excitation in a self-assembled unlinked antenna

The organic-terbium hybrid compound designed with the azido molecule L, 2-methoxy benzoic acid tris-(2-methoxybenzoyl)hydrazide, exhibits three-photon-excited green emission as well as second-harmonic generation even though the antenna is unlinked from the metal center.     

The specific fluorimetric determination of digoxin.

The simultaneous determination of Cd, Cu, Pb and Zn in lead and zinc concentrates by fundamental, second-harmonic and linear-sweep a.c. and pulse polarographic methods is described. Calibration curves are linear over wide concentration ranges, so that both major and minor trace constituents can be determined in the same experiment; thus the polarographic method is highly competitive with atomic absorption spectrometry (a.a.s.). Conventional a.c. polarography and a.a.s. were compared in the first instance with conservative instrumentation. More sophisticated polarographic methods were then utilized; with the phase-selective linear sweep a.c. (fundamental- and second-harmonic) methods the four elements were determined simultaneously from voltammograms obtained in less than 20 s down to the 10^-6-10^-7M concentration range.     

Effect of the structure of a ferroelectric vinylidene fluoride-tetrafluoroethylene copolymer on the characteristics of a local piezoelectric response

The surface topography and characteristics of a local piezoelectric-response signal in isotropic films of a ferroelectric vinylidene fluoride-tetrafluoroethylene copolymer with a composition of 94: 6 are studied via scanning probe microscopy. The X-ray diffraction and IR spectroscopy data indicate that crystallization occurs in a mixture of β and γ polymorphic modifications. The exposure of the original film to a dc field bipolar leads to the formation of polarized regions exhibiting low stability. Recrystallization is followed by structural transformations accompanied by conformational transitions. As a result, there is a decrease in the concentration of chain segments in the T₃GT₃G^? conformation and, conversely, an increase in the concentration of isomers in the planar zigzag conformation. In addition, the characteristics of the local piezoelectric response after polarization become more stable, while the signal undergoes phase reversal. A second-harmonic piezoelectric response signal induced by the electrostriction effect is detected for the studied ferroelectric polymer samples. It is found that the original film has two types of regions that contribute to the measured signal. A change in the pattern of the second-harmonic piezoelectric-response signal in the recrystallized film is attributed to a change in the contribution of the electrostriction effect to the macroscopic piezoelectric response.     

In situ Second-Harmonic Generation Circular Dichroism with Submonolayer Sensitivity

In this work, we present an experimental setup for the in situ and ex situ study of the optical activity of samples, which can be prepared under ultra-high vacuum (UHV) conditions by second-harmonic generation circular dichroism (SHG-CD) over a broad spectral range. The use of a racemic mixture as a qualified reference for the anisotropy factor is described and, as an example, the chiroptical properties of 1.5 μm thick (multilayers) as well as sub-monolayer thin films of the R- and S-enantiomer of 1,1′-Bi-2-naphthol (BINOL) evaporated onto BK7 substrates were investigated.     

Synthesis and photophysical properties of soluble polyimides and polyquinazolones containing side-chain chalcones or azo chromophores

Soluble aromatic and carboxyl- and hydroxyl-containing polyimides, mixed polyimides, and polyquinazolones of various chemical structures, as well as a series of new dicyanoazobenzene chromophores, are synthesized. From 20 to 80 mol % of chromophore groups are incorporated into side chains of the polymers. The thermal, photosensitive, and nonlinear optical properties (second-harmonic generation) of the chromophore-containing polymers are investigated. The polymers with covalently attached groups of the dye DR-13 or azo-derivatives of 4-phthalonitrile demonstrate the highest nonlinearity. The T _g values of the polyimides vary from 165 to 215°C; their temperatures corresponding to 5% weight loss lie in the range 290–350°C; and the measured coefficients of second-harmonic generation, d ₃₃, for a number of polarized films based on chromophore-containing polymers attain several tens of picometers per volt. The incorporation of chromophore groups into the side chains of the polymers causes an increase in the photosensitivity of polyimides by an order of magnitude relative to that of the parent polymers (S _0.1 = (3?4) × 10⁵ cm²/J in the range of dye absorption).     

Reversible two-photon optical data storage in coumarin-based copolymers

A functionalized polymer film allowing for a complete and straightforward second-harmonic generation (SHG)-assisted high-contrast writing-reading-erasing-writing sequence is proposed. The whole process is supported by the reversible photoinduced dimerization of a coumarin chromophore and enables efficient optical data storage that can be detected only by SHG imaging.     

Bulk characterization methods for non-centrosymmetric materials: second-harmonic generation, piezoelectricity, pyroelectricity, and ferroelectricity

Characterization methods for bulk non-centrosymmetric compounds are described. These methods include second-harmonic generation, piezoelectricity, pyroelectricity, and ferroelectricity. In this tutorial review with each phenomenon, details are given of the measurement techniques along with a brief history and background. Finally, data interpretation is discussed.     

Amphiphilic dyes for NLO in LB-films

The influence of structural variations of phenyl-hydrazones and stilbazium salts on monolayer behaviour and second-harmonic generation in LB-monolayers is discussed. In contrast to the stilbazium salts the variation of the substituents of the phenylhydrazones does not influence the absorption maximum of the dyes in resonance enhancement of the nonlinearity. This allows a direct comparison of the substitution pattern on SHG.     

Probing molecules adsorbed at the surface of nanometer colloidal particles by optical second-harmonic generation

It is observed that optical second-harmonic generation from molecules adsorbed at the surface of nanometer size colloidal particles occurs at angles as large as 90 degrees away from the fundamental beam direction. This phenomenon can be rigorously described by the nonlinear Rayleigh-Gans-Debye theory and used for probing molecules adsorbed on nanometer size colloidal particles.     

Determining the second-harmonic signal in electrochemical systems

Processes of adsorption and desorption of the butanol-1, butanol-2, hexanol, pentanol, and isoamyl alcohol molecules on a mercury electrode are studied with use made of the method of a second-harmonic signal in the region of radiowave frequencies. Two potentials are simultaneously applied to the metal/solution interface, specifically, a constant potential and a weak variable potential. The magnitude of the constant potential is close to the corresponding potential of adsorption and the variable potential has an amplitude in the limits of 2 to 20 mV and a frequency varying from a few tens of hertzs to a few tens of kilohertzs. Despite the absence of charge transport during the adsorption between the alcohol molecules and the electrode, the quadratic dependence between a signal of electromagnetic radiation of the radiowave frequencies U and the amplitude of the variable potential E _v1 applied to the metal/solution interface is discovered for all peaks in the curves of the second-harmonic signal for various concentrations of alcohols, various frequencies, and various values of the amplitude of the variable potential. Investigations for systems containing chlorides of sodium, potassium, and cesium in addition to ethylene glycol are conducted. According to an analysis of obtained experimental data, the number of peaks increases with decreasing concentration of chlorides, whereas the size of the sodium, potassium, and cesium cations makes no impact on the magnitude of the emitted signal. At the same time, diminishing the concentration of the chlorides leads to a certain amplification of the signal.     

Nonlinear response theory with relaxation: the first-order hyperpolarizability

Based on the Ehrenfest theorem, an equation of motion that takes relaxation into account has been presented in wave-function theory, and the resulting response functions are nondivergent in the off-resonant as well as the resonant regions of optical frequencies. The derivation includes single- and multideterminant reference states. When applied to electric dipole properties, the response functions correspond to the phenomenological sum-over-states expressions of Orr and Ward [Mol. Phys. 20, 513 (1971)] for polarizabilities and hyperpolarizabilities of an isolated system. A universal dispersion formula is derived for the complex second-order response function. Response theory calculations are performed on lithium hydride and para-nitroaniline for off-resonant and resonant frequencies in the electro-optical Kerr effect and second-harmonic generation.