A. V. Kityk

Capillary rise of water in hydrophilic nanopores.

We report on the capillary rise of water in three-dimensional networks of hydrophilic silica pores with 3.5 nm and 5 nm mean radii, respectively (porous Vycor monoliths). We find classical square root of time Lucas-Washburn laws for the imbibition dynamics over the entire capillary rise times of up to 16 h investigated. Provided we assume two preadsorbed strongly bound layers of water molecules resting at the silica walls, which corresponds to a negative velocity slip length of -0.5 nm for water flow in silica nanopores, we can describe the filling process by a retained fluidity and capillarity of water in the pore center. This anticipated partitioning in two dynamic components reflects the structural-thermodynamic partitioning in strongly silica bound water layers and capillary condensed water in the pore center which is documented by sorption isotherm measurements.

Continuous Paranematic-to-Nematic Ordering Transitions of Liquid Crystals in Tubular Silica Nanochannels

The optical birefringence of rodlike nematogens (7CB, 8CB), imbibed in parallel silica channels with 10 nm diameter and 300 microm length, is measured and compared to the thermotropic bulk behavior. The orientational order of the confined liquid crystals, quantified by the uniaxial nematic ordering parameter, evolves continuously between paranematic and nematic states, in contrast to the discontinuous isotropic-to-nematic bulk phase transitions. A Landau-de Gennes model reveals that the strength of the orientational ordering fields, imposed by the silica walls, is beyond a critical threshold, that separates discontinuous from continuous paranematic-to-nematic behavior. Quenched disorder effects, attributable to wall irregularities, leave the transition temperatures affected only marginally, despite the strong ordering fields in the channels.

Anomalous front broadening during spontaneous imbibition in a matrix with elongated pores

During spontaneous imbibition, a wetting liquid is drawn into a porous medium by capillary forces. In systems with comparable pore length and diameter, such as paper and sand, the front of the propagating liquid forms a continuous interface. Sections of this interface advance in a highly correlated manner due to an effective surface tension, which restricts front broadening. Here we investigate water imbibition in a nanoporous glass (Vycor) in which the pores are much longer than they are wide. In this case, no continuous liquid–vapor interface with coalesced menisci can form. Anomalously fast imbibition front roughening is experimentally observed by neutron imaging. We propose a theoretical pore-network model, whose structural details are adapted to the microscopic pore structure of Vycor glass and show that it displays the same large-scale roughening characteristics as observed in the experiment. The model predicts that menisci movements are uncorrelated, indicating that despite the connectivity of the network the smoothening effect of surface tension on the imbibition front roughening is negligible. These results suggest a new universality class of imbibition behavior, which is expected to occur in any matrix with elongated, interconnected pores of random radii.

Complete sets of elastic constants and photoelastic coefficients of pure and MgO-doped lithium niobate crystals at room temperature

This paper presents the results of ultrasonic measurements of LiNbO3 and LiNbO3:MgO crystals. The tensors of piezoelectric coefficients, elastic stiffness constants, and elastic compliances are determined for both crystals at room temperature. Combining these data with the results of piezo-optical measurements, a complete set of photoelastic tensor coefficients is also calculated. Doping of LiNbO3 crystals by MgO does not lead to a considerable modification of their elastic and photoelastic properties. However, LiNbO3:MgO is characterized by a considerably higher resistance with respect to powerful light radiation, making it promising for future application in acousto-optic devices that deal with superpowerful laser radiation. Presented here are the complete tensor sets of elastic constants and photoelastic coefficients of LiNbO3 and LiNbO3:MgO crystals that may be used for a geometry optimization of acousto-optical interaction providing the best diffraction efficiency of acousto-optical cells made of the...

Absorption and fluorescence spectra of heterocyclic isomers from long-range-corrected density functional theory in polarizable continuum approach.

Long-range-corrected (LC) DFT/TDDFT methods may provide adequate description of ground and excited state properties; however, accuracy of such an approach depends much on a range separation (exchange screening) representing adjustable model parameter. Its relation to a size or specific of molecular systems has been explored in numerous studies, whereas the effect of solvent environment is usually ignored during the evaluation of state properties. To benchmark and assess the quality of the LC-DFT/TDDFT formalism, we report the optical absorption and fluorescence emission energies of organic heterocyclic isomers, DPIPQ and PTNA, calculated by LC-BLYP DFT/TDDFT method in the polarizable continuum (PCM) approach. The calculations are compared with the optical absorption and fluorescence spectra measured in organic solvents of different polarity. Despite a considerable structural difference, both dyes exhibit quite similar range separations being somewhat different for the optical absorption and fluorescence emission processes. Properly parametrized LC-BLYP xc-potential well reproduces basic features of the optical absorption spectra including the electronic transitions to higher excited states. The DFT/TDDFT/PCM analysis correctly predicts the solvation trends although solvatochromic shifts of the electronic transition energies appear to be evidently underestimated in most cases, especially for the fluorescence emission. Considering the discrepancy between the experiment and theory, evaluated state dipole moments and solvation corrections to the exchange screening are analyzed. The results of the present study emphasize the importance of a solvent-dependent range separation in DFT/TDDFT/PCM calculations for investigating excited state properties.

Spatial anisotropy of the acousto-optical efficiency in lithium niobate crystals

We report the spatial anisotropy of the acousto-optic (AO) figure of merit M2 in LiNbO3 crystals. The analysis is based on the indicative surfaces being calculated for several geometries of the AO diffraction. Basing on these results the most efficient geometries of AO cells made of LiNbO3 crystals are determined. It is revealed that the cells made of certain nondirect crystal cuts provide several times better AO diffraction efficiency comparing to the traditional ones, i.e., made of direct cuts of LiNbO3. The obtained results present considerable practical interest since may be useful in a designing of highly efficient AO cells made of LiNbO3 crystals. The methodology developed in the present work may be applied to other crystal materials as well.

Piezo-optic coefficients of MgO-doped LiNbO3 crystals.

We describe an interferometric technique suitable for determination of piezo-optic coefficients (POCs) in crystals. The method considers real nonparallelism of measured samples, thereby improving the measuring precision of POCs significantly. Corresponding equations are derived for the interferometric half-wave stress method. Using this technique we have determined a complete set of POCs of pure and MgO-doped LiNbO(3) crystals. The reliability of the data has been confirmed by comparing the effective POCs expressed through the combinations of measured POCs and the effective POCs determined independently using highly precise optical birefringence measurements. Pure and MgO-doped LiNbO(3) crystals reveal nearly the same magnitudes of POCs. However, LiNbO(3):MgO exhibits about 4 times higher resistance with respect to powerful light radiation, making it more suitable for application in acousto-optic devices that deal with superpowerful laser radiation.

UV–vis spectroscopy and semiempirical quantum chemical studies on methyl derivatives of annulated analogues of azafluoranthene and azulene dyes

Paper reports the measured optical absorption and fluorescence spectra of 4-(2-chlorophenyl)-7-methyl-1,3-diphenyl-1H-pyrazolo[3,4-b]quinoline (MCPDPPQ), as well as 6-methyl-1,3-diphenyl-3H-indeno[1,2,3-de]pyrazolo[3,4-b]quinoline (MDPIPQ) and 9-methyl-6-phenyl-6H-5,6,7-triazadibenzo[f,h]naphtho[3,2,1-cd]azulene (MPTNA) representing cyclized five- or seven-membered regioisomeric products of MCPDPPQ, respectively. The spectra has been recorded in solvents of different polarity and compared with the results of quantum chemical calculations performed by means of the semiempirical method PM3 in combination with molecular dynamics (MD) simulations. Cyclization of MCPDPPQ into MDPIPQ or MPTNA is accompanied by a significant red shift of the first optical absorption and fluorescence bands. While the solvent polarity rises all the dyes exhibit the blue shift of the first absorption band and the red shift of the fluorescence band. These trends have been reproduced within the semiempirical calculations in combination with the Lippert-Mataga dielectric polarization model and explained by specific orientations of the dipole moments in the ground and excited states. All dyes may be considered as candidates for the luminescent or electroluminescent applications. Depending on solvent polarity they emit light in the green-yellow range of the visible spectra.

Thermotropic nematic and smectic order in silica glass nanochannels

Optical birefringence measurements on a rodlike liquid crystal, octyloxycyanobiphenyl, imbibed in silica channels (7 nm diameter), are presented and compared to the thermotropic bulk behavior. The orientational and positional order of the confined liquid evolves continuously at the paranematic-to-nematic and sizeably broadened at the nematic-to-smectic order transition, respectively, in contrast to the discontinuous and well-defined second-order character of the bulk transitions. A Landau–de Gennes analysis reveals identical strengths of the nematic and smectic ordering fields (imposed by the walls) and indicates that the smectic order is more affected by quenched disorder (originating in channel tortuosity and roughness) than the nematic transition.

Photoelastic and acousto-optical properties of Cs 2 HgCl 4 crystals

We use a Mach-Zehdner interferometric technique to study the piezo-optical properties of Cs2HgCl4 crystals at room temperature. All piezo-optical (pi(mn)) and photoelastic (p(in)) tensor constants are obtained. A substantial photoelastic effect and low ultrasonic velocities in these crystals determine a relatively high figure of merit M2 for isotropic diffraction (for a certain geometry of acousto-optical interactions, M2 approximately 110 x 10(-15) s3/kg). The new material may be considered, therefore, a candidate for applications in acousto-optical devices. The dependence of the acoustic walk-off angle on the direction of sound propagation is calculated for the principal crystallographic planes.