Numerical Simulations of femtosecond-laser-induced dynamic alignment of molecules in the high-frequency off-resonance regime

The motion equation for ? between the molecular axis and laser polarization direction in a high-frequency off-resonance femtosecond laser field is deduced while simultaneously examining the effects of a permanent dipole moment and field-induced polarizability and hyperpolarizability to molecular rotation. Femtosecond-laser-induced dynamic alignment of CO, N₂, and Br₂ molecules are investigated by numerically solving the obtained rotation equation for the angle ?. The effects of the molecular permanent dipole moment and the field-induced polarizability and hyperpolarizability on the degree of alignment are presented at different intensities. Our computational results show that the dynamic alignment of molecules is primarily determined by field-induced polarizability and the second hyperpolarizability for the laser intensity range from 5 × 10¹⁴ to 5 × 10¹⁶ W/cm². The contributions of higher order correction terms to molecular alignment can usually be neglected. The polarizability-field interaction makes the angular distributions of a molecule have a maximum along the polarization axis and a minimum perpendicular to it. The role of the second hyperpolarizability keeps the molecular counts maximum along the laser polarization direction but minimum at an angle of 45° between the molecular axis and the polarization direction. There is also a second maximum of molecular counts perpendicular to the polarization axis. For CO, N₂, and Br₂ molecules, the dependences of laser-induced dynamic alignment on laser intensity exhibit completely different characteristics.     

Mechanochemical synthesis of noncentrosymmetric compounds in oxide systems

We study the influence of anomalous anisotropy in the elastic constants of paratellurite (α-TeO₂) on the rate of the following mechanochemical reactions: Bi₂O₃ + SeO₂ = BiSeO₅; Bi₂O₃ + TeO₂ = Bi₂TeO₅; SeO₂ + TeO₂ = TeSeO₄. The formation of the following compounds was registered by means of X-ray analysis and thermal annealing: Bi₆SeO₁₁, Bi₂TeO₅, and TeSeO₄.     

Polarizability of two interacting molecules N<Subscript>2</Subscript> and O<Subscript>2</Subscript>

In the context of the Silberstein theory, by introducing model atoms, the polarizability of pairs of interacting molecules N₂-N₂, O₂-O₂, and N₂-O₂ was studied in relation to the mutual orientation and the intermolecular distance of the molecules in the pairs. The polarizability tensor for the equilibrium configurations of the (N₂)₂ and (O₂)₂ dimers was calculated.     

Electrical properties of Na<Subscript>2</Subscript>SO<Subscript>4</Subscript>-based composite systems

Composite electrolytes are well-known multiphase systems and exhibit maxima in the conductivity at certain second-phase concentration. An attempt has been made to investigate a number of sodium sulfate (Na₂SO₄)-based composite systems. The dispersoids that have been used are MgO, Al₂O₃, and SiO₂. The samples have been characterized using impedance spectroscopy, X-ray diffraction, and differential scanning calorimetry. The maximum conductivity has been observed for MgO dispersed system, and the percolation threshold has been observed at 30-mol% dispersoid, MgO concentration. Interestingly, two maxima have been observed in case of the Na₂SO₄–SiO₂ and Na₂SO₄–Al₂O₃ composite systems. In the Na₂SO₄–SiO₂ system, the first maximum occurs at lower concentration, i.e., in the range between 10 and 20 mol%, whereas the second occurs at the 40-mol% dispersoid concentration. For the Na₂SO₄–Al₂O₃ system, although slightly indistinguishable, two peaks in the conductivity vs composition plot have been observed around 12- and 30-mol% Al₂O₃ concentrations.     

Enhancement of antiferromagnetic interaction and transition temperature in M<Subscript>3</Subscript>TeO<Subscript>6</Subscript> systems (M = Mn,Co, Ni,Cu)

Several M₃TeO₆ (M = Mn, Co, Ni, Cu) oxides order antiferromagnetically at low temperatures (?60 K), while displaying interesting dielectric properties at high temperatures (ferroelectricity below 1000 K in M = Ni case). We have investigated and analyzed the structural and magnetic properties of Mn-doped Co₃TeO₆ and Ni₃TeO₆, which order antiferromagnetically at temperatures higher than their undoped counterparts.     

Effect of molecular weight of PMMA on the conductivity and viscosity behavior of polymer gel electrolytes containing NH<Subscript>4</Subscript>CF<Subscript>3</Subscript>SO<Subscript>3</Subscript>

The addition of polymethyl methacrylate (PMMA) having different molecular weights to electrolytes containing ammonium trifluoromethanesulfonate (NH₄CF₃SO₃) in diethyl carbonate (DEC) has been found to result in conductivity enhancement and to yield gel electrolytes with conductivity higher than the corresponding liquid electrolytes. The increase in conductivity has been found to be due to the dissociation of undissociated NH₄CF₃SO₃ and ion aggregates present in the electrolytes, and this has been supported by Fourier transform infrared spectroscopy results, which suggests active interaction of PMMA and NH₄CF₃SO₃ in these gel electrolytes. The increase in conductivity also depends upon the molecular weight of the polymer used and is relatively more for PMMA having lower molecular weight. The increase in viscosity with PMMA addition also depends upon the molecular weight of the polymer and is closely related to the conductivity behavior of these electrolytes. Polymer gel electrolytes have been found to be thermally stable up to a temperature of 125 °C.     

Phase behaviour and superionic phase transition in K<Subscript>3</Subscript>H(SeO<Subscript>4</Subscript>)<Subscript>2</Subscript>

The phase behaviour of K₃H(SeO₄)₂ (TKHSe) above room temperature has been studied by differential scanning calorimetric (DSC), thermogravimetric analysis (TGA), simultaneous thermogravimetric and mass spectroscopy analysis (TG-MS), impedance spectroscopy (IS) and X-ray powder diffraction (XRD). Our results show that the previously claimed superionic phase transition in TKHSe at around 388 K (114.85 °C) is also the onset temperature of a slow thermal dehydration that occurs at reaction sites distributed over the surface of the crystal. That is, we propose that the TKHSe undergoes simultaneously a superionic phase transition and a decomposition process with a very slow reaction rate that is evident when the sample is pulverized to fine powder, both starting at the same temperature. As a matter of fact, we observe a decrease of the magnitude of the dc-conductivity on successive thermal runs in powdered sample attributed to sample decomposition that starts at the surface of the TKHSe grains, but the jump in conductivity is only a consequence of the order–disorder transition in the TKHSe phase that remains inside the grains.     

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.     

Effect of uniaxial pressure on the infrared spectra of (NH<Subscript>4</Subscript>)<Subscript>2</Subscript>SO<Subscript>4</Subscript> crystals

The infrared reflectance spectra of a mechanically free or uniaxial-pressure-confined (NH₄)₂SO₄ crystal were studied for the first time in the spectral range 800–1700 cm^?1 in three crystallographic directions. Using the Kramers-Kronig relations, the dispersion and pressure dependences of the following quantities are obtained: the index of refraction n, the real (?₁) and imaginary (?₂) parts of the permittivity, the frequencies of longitudinal (ω_LO) and transverse (ω_TO) optical vibrations, the damping constant γ, and the oscillator strength f of the mechanically free or clamped (NH₄)₂SO₄ crystal. A considerable change in the main reflection bands with pressure was observed, which is due to the effect of uniaxial pressure on the NH₄ and SO₄ tetrahedral frames.     

Investigation of electrical and optical properties of ZnO thin films grown with O<Subscript>2</Subscript>/O<Subscript>3</Subscript> gas mixture

The electrical and optical properties of ZnO thin films grown with an O₂/O₃ gas mixture are compared with samples grown with pure oxygen gas. The ZnO films were grown on sapphire(0001) by pulsed laser deposition. The residual background carrier concentration is reduced by using an O₂/O₃ gas mixture as compared to pure molecular oxygen. In particular, a one order of magnitude reduction in residual background carrier density (6.15×10¹⁶ cm^-3) is achieved by using an O₂/O₃ gas mixture. The lower donor defect density is attributed to the generation of acceptor defects compensating for the residual donor defects. Photoluminescence results show that the deep level emission increased and the band edge emission decreased for the ZnO films grown with ozone, as compared to the samples grown with pure oxygen gas. PACS 73.61.Ga; 78.55Et; 81.05 Dz; 81.15.Fg     

Third-order optical nonlinearity of a novel material: [(C<Subscript>4</Subscript>H<Subscript>9</Subscript>)<Subscript>4</Subscript>N][Co(dmit)<Subscript>2</Subscript>]

A novel dmit organometallic complex—[(C₄H₉)₄N][Co(dmit)₂] (dmit^2? = 4,5-dithiolate-1,3-dithiole-2-thione), abbreviated as BuCo, is synthesized and its third-order optical nonlinearity of the acetone solution is characterized using the Z-scan technique with a 40-ps pulse width at 1064 nm. Z-scan curves show that BuCo sample solution possesses the negative nonlinear refraction, exhibiting a self-defocusing effect. In addition, the two-photon absorption has been observed in BuCo. The effective molecular second-order hyperpolarizability γ_eff of the BuCo molecule was estimated to be as large as 5.60 × 10^?31 esu, suggesting BuCo is a potential material for optical device applications.     

Acoustogyration diffraction of optical waves: case of SiO<Subscript>2</Subscript> and TeO<Subscript>2</Subscript> crystals

Interaction of acoustic and light waves with accounting for elastooptic and elastogyration effects is theoretically described. Collinear acoustogyration diffraction in quartz and paratellurite crystals is experimentally investigated and thoroughly analyzed. Piezogyration effect is experimentally studied for TeO₂ crystals. The acoustogyration efficiency and the acoustogyration figure of merit calculated for a number of crystals (GaAs, TeO₂ and SiO₂) are shown to be too small for experimental detection. On the other hand, we demonstrate that the light diffraction at periodical distribution of the imaginary part of dielectric permittivity related to the piezogyration effect should, in principle, be observed for the case of interaction of optical waves with enantiomorphous ferroelastic domain structure and in cholesteric liquid crystals.     

Evaluation of optical parameters of some tellurite glasses

Evaluation of optical parameters of tellurite glasses in the form: 80TeO₂-5TiO₂-(15-x) WO₃-xA_nO_m, where xA_nO_m = 0.01, 1, 3, 5 Nb₂O₅ or 0.01, 0.1, 1, 3 Nd₂O₃ or 0.01, 0.1, 1, 3, 5, 7 Er₂O₃ mol% will be carried out. The optical parameters will be focused on calculating molar refractivity, molar polarizability, oxide ion polarizability, molar cation polarizability, optical basicity, metallization and number of polarizable atoms per unit volume for every glass composition in order to interpret the refractive index of these glasses.     

Stability of C<Subscript>20</Subscript> fullerene chains

The stability of (C₂₀)_N metastable chains, where C₂₀ fullerenes are joined by tight covalent bonds, is analyzed by numerical simulation using a tight-binding potential. Various channels of losing the chain-cluster structure of the (C₂₀)_N complexes have been determined including the decay of the C₂₀ clusters, their coalescence, and the separation of one C₂₀ fullerene from a chain. The lifetimes of the (C₂₀)_N chains with N = 3–7 for T = 2000–3500 K are directly calculated by the molecular dynamics method. It has been shown that, although the stability of the chains decreases with an increase in N, it remains sufficiently high even for N ? 1. An interesting lateral result is the observation of new (C₂₀)_N isomers with the combination of various intercluster bonds with the maximum binding energy of fullerenes in the chain.     

S<Subscript>3</Subscript> symmetry and neutrino masses and mixings

Based on the universal seesaw mass matrix model with the three scalars φ_i, and by assuming S₃ flavor symmetry for the Yukawa interactions, the lepton masses and mixings are investigated systematically. In order to understand the observed neutrino mixing, the charged leptons (e,μ,τ) are regarded as the three objects (e₁,e₂,e₃) of S₃, while the neutrino mass eigenstates are regarded as the irreducible representation (ν_η,ν_σ,ν_π) of S₃, where (ν_π,ν_η) and ν_σ are a doublet and a singlet, respectively, which are composed of the three objects (ν₁,ν₂,ν₃) of S₃.     

Frequency measurements in the b <Superscript>3</Superscript>Π(0<Subscript>u</Subscript><Superscript>+</Superscript>) - X <Superscript>1</Superscript>Σ<Subscript>g</Subscript><Superscript>+</Superscript> system of K<Subscript>2</Subscript>

Absolute transition frequencies of the b ³Π(0_u ⁺) - X ¹Σ_g ⁺ system of K₂ were measured in a molecular beam with Lamb dip absorption spectroscopy applying a frequency comb from a femtosecond pulsed laser. Both, K atoms and K₂ molecules are present in the beam and are expected to interact by collisions. The atoms can be deflected optically out of the beam, and thus the collision rate between K atoms and K₂ molecules is changed by about an order of magnitude. The molecular transition frequencies for low collisional rate are compared with those for high one. Limits for the collisional frequency shift within the beam are determined.     

Static (hyper)polarizabilities and absorption spectra of single [2.2]<Emphasis Type="Italic">p</Emphasis>-cyclophane NO<Subscript>2</Subscript>/NH<Subscript>2</Subscript> substituted from DFT methods

We explore the behavior of the average of polarizability (< α >), total first hyperpolarizability (β_total) and average of second hyperpolarizability (< γ >) for single A/D (-NO₂/-NH₂) substituted [2.2]p-cyclophane. The geometric optimization was carried out at HF and DFT (SVWN, PBE, B3LYP, PBE0, BHHLYP and CAM-B3LYP) level, in gas phase, using the 6-31 + G(d,p) basis set. The static tensor components of < α > and β_total, in gas phase, were calculated using Field Finite (FF) methods with electric field intensities of E = ± 0.001 a.u. in each (x,y,z) axis direction. The substitution of A/D groups in positions 7–15 (structure 2 in Fig. 1) produced an increment in the < α > values. Regardless of the A/D positions, the < α > values showed not significant changes at all theory level. < α > DFT results are overestimated up to 20%, if HF values are taken into account, being SVWN and PBE functionals those that give the main deviation. There are monotonic and progressive behaviors of β_total for the 1–5 structure change as expected by orientation of the dipolar moment in both aromatic rings. With respect to the performance of DFT functionals, < γ > and β_total results are significantly overestimated if HF values are taken into account. In fact, the relative percentage error of β_total at DFT level with respect to HF ones is between 58 and 132%, being PBE functional those that give the main deviation. The close overlap of the orbitals between the rings facilitates chromophore delocalization to account for the observation of high β_total in these compounds. Therefore, we expected that the contribution by coupling of the transition moment between first and higher excited states should be lie much higher due to phane effect than that for ring units.

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Fig. 1 a Single [2.2]p-cyclophane core molecule. b Geometric parameters of interest c Highlights for the 4, 7, 12, and 15 positions, which are substituted by (-NO₂/-NH₂) acceptor/donor pair

     

Vibrational spectra of rhombohedral TeO3 compared to those of ReO3‐like proto‐phase and α‐TeO2 (paratellurite): lattice dynamic and crystal chemistry aspects

Vibrational spectra of rhombohedral TeO₃ (r‐TeO₃) are analyzed along with those of ReO₃‐like proto‐phase (c‐TeO₃) and α‐TeO₂ (paratellurite), emphasizing their lattice dynamic and crystal chemistry aspects. It is shown that (1) r‐TeO₃ can be regarded as resulting from the condensation of a particular R‐point soft phonon of c‐TeO₃; (2) the Raman spectra of r‐TeO₃ and α‐TeO₂ are indicative of the two fundamentally different (from the crystal chemistry point of view) types of crystalline oxides, namely, framework‐type and island‐type, respectively. Copyright © 2010 John Wiley & Sons, Ltd.     

Effect of separation on second-order hyperpolarizability of two silver nanoclusters

We present a study on dielectric response of Ag₁₄ nanocluster dimer using first principles methods. The interaction energy, (hyper)polarizability of dimer are predicted under various separations of the two identical Ag₁₄ nanoclusters. The appropriate separation makes the second-order hyperpolarizability of Ag₁₄ dimer is about 70 times larger than the Ag₁₄ monomer. The increase of polarizability and hyperpolarizability is ascribed to reconfiguration of molecular electronic state from Ag cluster monomer to dimer. Nonlinear response is more susceptible to the steady intermediate state compared to linear response. The crucial transitions contributed to hyperpolarizability are assigned to be from highest occupied molecular orbitals to the lowest unoccupied molecular orbital (HOMOs-LUMO) of nanocluster dimer. Binding character of LUMO plays an important role in determining nonlinear optical properties.     

Third-order potential constants and dipole moment of SeO2 by microwave spectroscopy

The third-order potential constants of SeO₂ have been recalculated using the vibrational frequencies reported for matrix-isolated SeO₂. General trends of the constants are in good accord with the results obtained for other triatomic molecules, such as SO₂, O₃, and OF₂. The dipole moment was measured more accurately to be 2.62 ± 0.05 D.