Том 121, № 2 (2016)

The main aim of the present study is to evaluate the mutual effect of copper sample and turboflame in laser induced breakdown spectroscopy (LIBS) signal enhancement. The use of copper sample leads to a signal enhancement in CN (B²Σ⁺–X²Σ⁺) 384.2–388.4 nm molecular transition, N_742nm, N_744nm, N_746nm (a triplet generated by the fine splitting of the 2s²2p²(³P)3s–2s²2p²(³P)3p transition) and H_{α, 656.3 nm} (as a flame inductor) atomic lines analysis. Additionally, increase in copper sample temperature with flame can enhance the Cu atomic line intensities (as copper sample inductors). Moreover, in this paper, the comparison between turboflame and alcohol flame on LIBS analysis was studied. LIBS signal intensity variation in a turboflame and turboflame coupled with copper sample at different laser pulse energies indicated that the low laser pulse energy could be compensated by using a copper sample that is coupled with turboflame and improved LIBS signal enhancement. For flames analysis, the use of metal sample in LIBS method is demonstrated to be costeffective, compact, and capable of signal enhancement.

The electronic structure and spectral-luminescence properties of the dye merocyanine 540 have been calculated within the framework of the semiempirical quantum-chemical method of partial neglect of differential overlap (PNDO) with spectroscopic parameterization. The trans and cis conformations of the molecule, as well as the trans–cis photoisomerization process, have been considered. The calculation has been performed for an isolated molecule of the merocyanine 540 and its complex with water. The results of the calculation have been compared with the experimental spectral-luminescence characteristics of the molecule in different solvents. It has been shown that there is a good agreement between the calculated and experimental spectra, the nature of the excited states, and photoprocesses.

The effect of silver nanoparticles (AgNPs) that are adsorbed on the surface of the purple membranes of Halobacterium salinarium bacteria on the optical properties and functional peculiarities of the lightsensitive protein bacteriorhodopsin (BR) has been demonstrated for the first time. Two mechanisms of the effect of AgNPs on the protein photocycle have been demonstrated using Raman scattering, giant Raman scattering, flash photolysis, and atomic force microscopy. It has been shown that the nanoparticles in the immediate spatial vicinity of BR fix its photocycle at the stage where it was at the moment of interaction with the nanoparticles. At greater distances, which reach three radii of an AgNPs, they have a weaker effect on BR, under which it retains the ability to be involved in the photocycle, however, has its parameters significantly changed. Thus, in the case of wild-type BR the photocycle accelerates and for the BR-D96N mutant it becomes slower. The data that are obtained could be of significance for creation of such optoelectronic hybrid systems with BR, where the parameters of its photocycle can be controlled using NPs. The results of the study may also be used in the field of nanobioengineering research, which is directed to creation of unique materials with controlled properties for recording and storage of information, energy transformation, and identification and characterization of trace amounts of analytes.

Fluoridezirconate crystallohydrates ZnZrF₆ · nH₂O (n = 6–2) and anhydrous ZnZrF₆ are investigated by vibrational spectroscopy and thermography. The influence of the hydrate number on the structure of the cationic and anionic sublattices of the crystallohydrates is studied. The changes in the strength of HOH···F and HOH···O hydrogen bonds of coordinated and outer-sphere water molecules occurring with variations in the hydrate number are determined by changes in the IR spectra. The IR spectra of ZnZrF₆ · nH₂O (n =6, 4) compounds, which have isolated complex anions [ZrF₆]^2– in their structure, revealed a band with two peaks in the range of 3470–3430 cm^–1, which corresponds to stretching vibrations of coordinated water molecules. The spectra of ZnZrF₆ · nH₂O (n = 5, 3, 2, 1) crystallohydrates with a polymeric structure show a high-frequency shift of this band, which corresponds to weakening of hydrogen bonds. The vibrations of crystallization water molecules involved in the network of strong O–H···F and O–H···O hydrogen bonds manifest themselves in the spectra of ZnZrF₆ · nH₂O (n =5, 3) crystallohydrates by broad structureless bands in the region of stretching, bending, and libration vibrations.

4-((9,10-dioxo-9,10-dihydroanthracen-1-yl)oxy)-3-methoxybenzaldehyde has been synthesized in an attempt to obtain a new photochromic compound. The optimized molecular structure, mole fractions of title compound in trans and ana forms have been investigated. UV-visible spectra of the compound were also recorded. Upon irradiation with 300 nm light, the camel solid turned orange, in which a visible absorption band was observed at 475 nm. The electronic properties, such as HOMO, LUMO and band gap energies were obtained by the time-dependent DFT (TD-DFT) approach. The predicted nonlinear optical properties of the title compound are much greater than those of urea. Transition structures were calculated by QST3 and IRC methods which yielded the potential energy surface and activation energy.

Metal–carbon materials exhibiting surface-enhanced Raman scattering have been synthesized by laser irradiation of colloidal systems consisting of carbon and noble metal nanoparticles. The dependence of the Raman scattering intensity on the material composition and laser irradiation conditions has been investigated. The possibility of recording the Raman spectrum of organic dye rhodamine 6G, deposited in amount of 10^–6 M on the substrate obtained from a colloidal solution is demonstrated.

We have reported the measurement of third-order optical nonlinearity by antiresonant ring interferometric nonlinear spectroscopic (ARINS) technique and discussed its usefulness over other popular measuring techniques such as Z-scan, degenerate four wave mixing (DFWM) and third harmonic generation (THG). The measurement has been simulated theoretically by taking different numerical values as well as sign of δ, which is a key parameter of ARINS. The technique has been benchmarked using toluene and the theoretical simulation has been substantiated experimentally by measuring the nonlinear optical coefficients (n₂ and β) of two different samples. The disadvantages of the technique have also been discussed. However, a number of advantages of ARINS override its disadvantages and therefore, ARINS may be preferred over other measuring techniques for the measurement of nonlinear optical parameters.

An integral modification of the generalized point-matching method (GPMMi) in the electrostatic problem for axisymmetric particles is developed. Scalar potentials that determine electric fields are represented as expansions in terms of eigenfunctions of the Laplace operator in the spherical coordinate system. Unknown expansion coefficients are determined from infinite systems of linear algebraic equations (ISLAEs), which are obtained from the requirement of a minimum of the integrated residual in the boundary conditions on the particle surface. Matrix elements of ISLAEs and expansion coefficients of the “scattered” field at large index values are analyzed analytically and numerically. It is shown analytically that the applicability condition of the GPMMi coincides with that for the extended boundary conditions method (ЕВСМ). As model particles, oblate pseudospheroids \(r\left( \theta \right) = a\sqrt {1 - {^2}{{\cos }^2}\theta } ,\;{^2} = 1 - {\raise0.7ex\hbox{${{b^2}}$} \!\mathord{\left/ {\vphantom {{{b^2}} {{a_2}}}}\right.\kern-\nulldelimiterspace}\!\lower0.7ex\hbox{${{a_2}}$}} \geqslant 0\) with semiaxes a = 1 and b ≤ 1 are considered, which are obtained as a result of the inversion of prolate spheroids with the same semiaxes with respect to the coordinate origin. For pseudospheroids, the range of applicability of the considered methods is determined by the condition \({\raise0.7ex\hbox{$a$} \!\mathord{\left/ {\vphantom {a b}}\right.\kern-\nulldelimiterspace}\!\lower0.7ex\hbox{$b$}} < \sqrt 2 + 1\). Numerical calculations show that, as a rule, the ЕВСМ yields considerably more accurate results in this range, with the time consumption being substantially shorter. Beyond the ЕВСМ range of applicability, the GPMMi approach can yield reasonable results for the calculation of the polarizability, which should be considered as approximate and which should be verified with other approaches. For oblate nonconvex pseudospheroids (i.e., at \({\raise0.7ex\hbox{$a$} \!\mathord{\left/ {\vphantom {a b}}\right.\kern-\nulldelimiterspace}\!\lower0.7ex\hbox{$b$}} \geqslant \sqrt 2 \)), it is shown that the spheroidal model works well if pseudospheroids are replaced with ordinary “effective” oblate spheroids. Semiaxes a_ef and b_ef of the effective spheroids are determined from the requirement of the particle volumes, as well as from the equality of the maximal longitudinal and transverse dimensions of particles or their lengths. As a result, the polarizability of pseudospheroids can be calculated by simple explicit formulas with an error of about 0.5–2%.

Methods for monitoring the optical power of artificial refractive eye lenses (intraocular lenses) based on measuring focal lengths in air and in medium are analyzed. The methods for determining the refraction of diffractive–refractive lenses (in particular, of MIOL-Akkord type), with allowance for the specific features of the diffractive structure, are considered. A computer simulation of the measurement of the focal length of MIOL-Akkord lenses is performed. The effective optical power of the diffractive component of these lenses is shown to depend on the diaphragm diameter. The optimal diaphragm diameter, at which spherical aberrations do not affect the position of foci, is found to be 3 mm. Possible errors in measuring the focal lengths are analyzed, and the necessary corrections that must be introduced into measurement results and calculations of refractions are determined.