Solvatochromic Effect on the Photophysical Properties of Two Coumarins

The absorption and emission spectra of two coumarins namely 7, 8 benzo-4-azidomethyl coumarin (C₁) and 6-methoxy-4-azidomethyl coumarin (C₂) have been recorded at room temperature in solvents of different polarities. The ground state dipole moments (μ _g ) of two coumarins were determined experimentally by Guggenheim method. The exited state (μ _e ) dipole moments were estimated from Lippert’s, Bakhshievs and Chamma-Viallet’s equations by using the variation of Stoke’s shift with the solvent dielectric constant and refractive index. The ground and excited state dipole moments were calculated by means of solvatochromic shift method and also the excited state dipole moments are determined in combination with ground state dipole moments. It was observed that dipole moments of excited state were higher than those of the ground state, indicating a substantial redistribution of the π-electron densities in a more polar excited state for two coumarins.     

Raman and infrared intensity analysis of CHCl3 and CDCl3

Raman and infrared intensity analysis of CHCl₃ is attempted to determine the bond polarisability derivatives and bond dipole moments and their derivatives respectively, on lines expained in our earlier papers.     

Dielectric alignment of a non-polar molecule substituting a polar molecule in a lattice of molecular dipoles

The dielectric alignment of a dilute non-polar component in a polar solvent may be determined by NMR spectroscopy. In this paper a series expansion of the alignment up to second order terms in the dipolar interaction is presented for a non-polar molecule replacing a single polar molecule in a rigid lattice of molecular dipoles. Assuming isotropic polarizabilities for all molecules Van Vleck earlier applied the lattice model in a theory of the dielectric constant of a dilute solution.In the present calculation the polarizabilities of the non-polar molecule and the dipoles are assumed to be anisotropic and isotropic, respectively. The anisotropy of the non-polar molecule is relevant, since the value of the alignment is zero for the isotropic case. Different results are obtained for cubic lattices and for a lattice points are uniformly distributed.In absence of a rigid dipole moment of the solvent molecules the latter formula may be compared with that implicity deduced by Buckingham for the Kerr effect. In the limit of strong dipoles the orientation imposed by the rigid dipole moments appears to be the major contribution to the alignment of the non-polar molecule.     

Photophysical characteristics of three novel benzanthrone derivatives: Experimental and theoretical estimation of dipole moments

The effect of solvents on absorption and fluorescence spectra and dipole moments of novel benzanthrone derivatives such as 3-N-(N′,N′-Dimethylformamidino) benzanthrone (1), 3-N-(N′,N′-Diethylacetamidino) benzanthrone (2) and 3-morpholinobenzanthrone (3) have been studied in various solvents. The fluorescence lifetime of the dyes (1-3) in chloroform were also recorded. Bathochromic shift observed in the absorption and fluorescence spectra of these molecules with increasing solvent polarity indicates that the transitions involved are π→π^?. Using the theory of solvatochromism, the difference in the excited-state (μ_e) and the ground-state (μ_e) dipole moments was estimated from Lippert-Mataga, Bakhshiev, Kawski-Chamma-Viallet, and McRae equations by using the variation of Stokes shift with the solvent’s relative permittivity and refractive index. AM1 and PM6 semiempirical molecular calculations using MOPAC and ab-initio calculations at B3LYP/6-31 G^? level of theory using Gaussian 03 software were carried out to estimate the ground-state dipole moments and some other physicochemical properties. Further, the change in dipole moment value (Δμ) was also calculated by using the variation of Stokes shift with the molecular-microscopic empirical solvent polarity parameter (E_T^N). The excited-state dipole moments observed are larger than their ground-state counterparts, indicating a substantial redistribution of the π-electron densities in a more polar excited state for all the systems investigated.     

Dipole moments and the mechanism of molecular motion in a cyanobiphenyl-containing liquid-crystal monomer in a solution and in the bulk of the material in the absence of external orienting fields

The dipole moments and dielectric polarization relaxation of a low-molecular liquid-crystal monomer, namely, 4-[ω-(2-propenoyloxy)pentyloxy]-4′-cyanobiphenyl (CBO-5A), are investigated in a mesomorphic phase, an isotropic melt, and a chloroform solution in the absence of external orienting fields. Analysis of the dipole polarization of the CBO-5A monomer in the chloroform solution (x ₂ ～ 0.0566 mol/mol) demonstrates that the temperature dependences of the permittivity and the dipole moment measured with decreasing temperature are characteristic of molecular association with the Kirkwood factor g = 0.77. It is found that the Kirkwood factor g for the isotropic melt is 0.55. The values of g < 1 indicate the presence of associates with a tendency toward antiparallel orientation of the CBO-5A molecules in both the solution and the melt. Dielectric absorption of relaxation nature is observed in the chloroform solution at temperatures in the range from ?50 to ?20°C. Two relaxation processes of dipole polarization are observed in the isotropic and liquid-crystal phases of the CBO-5A monomer in the bulk of the material. Examination of the temperature dependences of the dielectric relaxation time revealed that molecules of the CBO-5A liquid-crystal monomer in the bulk can be involved in several types of motion occurring through either the local mechanism or the cooperative mechanism.     

Editorial

The solvent effects on the electronic absorption and emission fluorescence spectra for a series of chalcone cyclic analogues were studied. The singlet-state excited dipole moments and the ground state dipole moments of the cyclic chalcone analogues E-2- benzylidene-1-benzosuberone E-2-(4′-methoxybenzylidene)-1-benzosuberone E-2-(4′-dimethylaminobenzylidene)-1-benzosuberone were calculated by using solvatochromic shift method by means of equations using the variations of Stokes’ shift with the solvent's dielectric constant and refractive index values. It was found that the excited state dipole moments calculated by the solvatochromic shift method were greater than the ground state dipole moments indicating a substantial redistribution of the pi-electron densities in a more polar excited state for each derivative.     

Electrochemical study and electrodeposition of copper in the hydrophobic tri-n-octylmethylammonium chloride ionic liquid media

The electrodeposition of metallic Copper in binary mixture ionic liquid/organic solvent (tri-n-octylmethylammonium chloride (TOMAC))/chloroform (CHCl₃) was investigated. The electrochemical behavior of Cu(II) in TOMAC/CHCl₃ at glassy carbon working electrode at room temperature was studied by cyclic voltammetry and spectroscopy impedance. The results from the cyclic voltammetry showed that the electrodeposition of metallic Cu in the binary mixture ionic liquid/organic solvent was an irreversible process and was controlled by the diffusion of Cu(II) on a glassy carbon working electrode. The average value of αn_α was found to be 0.23 at 25 °C and the diffusion coefficient (D₀) of Cu(II) was calculated to be 7.12 10^− 9 cm²/s at room temperature. The performance of TOMAC ionic liquid such as internal resistance has been investigated with electrochemical impedance spectroscopy (EIS). The scanning electron microscopy (SEM) micrographs was used to observe that the copper plating was moderately dense and contains fine crystallites with average sizes of about 1 μm at room temperature. Energy dispersive X-ray analysis (EDAX) profile showed that the obtained film was copper.     

Application of a new perturbation theory to evaluate the shear and bulk viscosity coefficients

Three liquids, CH₃F, CH₃Cl and CHF₃, have been submitted to systematic investigation in the microwave and far infra-red frequency domains.

The studies have been extended over a gradual variation of temperature and density scanning the whole liquid range beneath the critical region. Accordingly, the relative location in time of absorption processes were observed to evolve towards each other as the liquids expand when approaching their critical region.

We discuss the dielectric relaxation processes and their characteristic times, together with some very important features from the very intense absorption in the far infra-red. The correlative dispersion is fitted by a distribution of resonances model. The occurrence of specific alignment effects are shown to be responsible for local enhancement of the dipole moments, resulting in excess of integrated intensities.

Throughout this report a direct presentation of the experimental features displays already a number of characteristics of molecular dynamics. Their analysis will be completed and refined through the correlation functions formalism developed in a following paper.     

Solvent Effect on Absorption and Fluorescence Spectra of Three Biologically Active Carboxamides (C<Subscript>1</Subscript>, C<Subscript>2</Subscript> and C<Subscript>3</Subscript>). Estimation of Ground and Excited State Dipole Moment from Solvatochromic Method Using Solvent Polarity Parameters

The absorption and fluorescence spectra of three Carboxamides namely (E)-2-(4-Chlorobenzylideneamino)-N-(2-chlorophenyl)-4, 5, 6, 7-tetrahydrobenzo[b]thiophene-3-carboxamide (C₁), (E)-N-(3-Chlorophenyl)-2-(3, 4-dimethoxybenzylideneamino)-4, 5, 6, 7-tetrahydrobenzo[b]thiophene-3-carboxamide (C₂) and (E)-N-(3-Chlorophenyl)-2-(3, 4, 5-trimethoxybenzylideneamino)-4, 5, 6, 7-tetrahydrobenzo[b]thiophene-3-carboxamide (C₃) have been recorded at room temperature in solvents of different polarities using dielectric constant (ε) and refractive index (n). Experimental ground (μ_g) and excited (μ_e) state dipole moments are estimated by means of solvatochromic shift method and also the excited dipole moments are estimated in combination with ground state dipole moments. It was estimated that dipole moments of the excited state were higher than those of the ground state of all three molecules. Further, the changes in dipole moment (Dm \Delta \mu ) were calculated both from solvatochromic shift method and on the basis of microscopic empirical solvent polarity parameter (E_T^N E_T^N ) and the values are compared.     

Photoinduced Electron Transfer From Carbazole to Halomethanes in a Gas Phase

Intermolecular photoinduced electron transfer (PET) in a gas phase was studied using carbazole vapor fluorescence quenching by halomethanes (CHCl₃, CH₂Br₂, CCl₄, CHBr₃). The fluorescence quenching rate constants k _q changing from 2.3·10⁵ sec^–1·torr^–1 in mixtures with CHCl₃ to 4.6·10⁶ sec^–1·torr^–1 in mixtures with CHBr₃ at a constant temperature of 403 K were estimated. The dependence of the carbazole fluorescence decay rates in the presence of halomethanes on the free energy change G during transfer of the electron from carbazole to halomethanes is considered. It is suggested to take into account the influence of the vibrational energy of the carbazole molecule E _vib and its temperature changes in estimation of the G values. The differences between PET in the gas and liquid phases were analyzed. It is found that for mixtures with CCl₄ and CHBr₃ the negative temperature dependence of k _q is observed, when the decay rates and efficiencies of the intermolecular PET decreased with temperature increase in the range 403–573 K, i.e. these mixtures the electron transfer is not a barrier-restricted process.     

Calculation and interpretation of vibrational spectra of halogen-substituted ethanes

The frequencies, forms of the normal vibrations, and the potential energy constants of the CH₃CHF₂, CH₃CHCl₂, and CH₃CHBr₂ molecules were calculated. The interpretation of the vibrational spectra existing in the literature was refined, and the characteristics of the force field in these molecules were established.     

Experimental Determination of Ground and Excited State Dipole Moments of N,N-Bis (2, 5-di-tert-butylphenyl)-3, 4:9, 10-perylenebis (dicarboximide) (DBPI) A Photostable Laser Dye

In the present work, the absorption, emission spectra and dipole moments(μ_g, μ_e) of N, N-bis (2, 5-di-tert-butylphenyl)-3, 4:9, 10- perylenebis (dicarboximide) (DBPI) have been studied in solvents of various polarities at room temperature. Using the methods of solvatochromism, the difference between the first excited singlet state (μ_e) and ground state (μ_g) dipole moments was estimated from Lippert – Mataga,, Bakhshiev, Kawski – Chamma – Viallet equations. The change in dipole moment (Δμ) was also calculated using the variation of the Stokes shift with microscopic solvent polarity parameter (E _T ^N ). It was observed that the value of excited singlet state dipole moment is higher (3.53 Debye) than the ground state one (1.92Debye), showing that the excited state of DBPI is more polar than the ground state.     

Effect of gamma radiation on the surface and bulk properties of poly(tetrafluoroethylene)

The effect of gamma radiation on the contact angle θ, the work of adhesion γ _SL for polar and nonpolar liquids, disperse and polar components of the surface energy γ _S , the magnitude of bulk dielectric polarization P ₀, and the dielectric increment Δε for sintered and non-sintered poly(tetrafluoroethylene) (PTFE) of suspension polymerization are studied. Sintered PTFE exhibits anomalously high growth of the studied parameters with an absorbed dose up to 500 kGy: Δε by more than four orders of magnitude, the work of adhesion of the polar liquid \(\gamma _{SL}^{{H_2}O}\) by a factor of 1.5, the polar component of the surface energy γ^pol _S by 20 times. The observed changes are found to be considerably larger than those expected from the viewpoint of the amplification of dipole–dipole and donor–acceptor molecular interactions with the participation of polar groups formed in poly(tetrafluoroethylene) upon irradiation. The similar behavior of Δε, \(\gamma _{SL}^{{H_2}O}\), and γ^pol _S parameters depending on the exposed dose and subsequent annealing of the samples at 150°C is revealed. A unified mechanism for changes in the bulk polarization and surface properties caused by the formation in poly(tetrafluoroethylene) of long-lived electron–hole pairs is suggested.     

Rotational Diffusion and Solvatochromic Correlation of Coumarin 6 Laser Dye

Rotational diffusion of coumarin 6 (C6) laser dye has been examined in n-decane and methanol as a function of temperature. The rotational reorientation of this probe has been measured in these solvents. It is observed that the decrease in viscosity of the solution is responsible for the decrease in the rotational relaxation time of the probe molecule. The molecule C6 has long reorientation times in n-decane solvent as compared to methanol over all temperatures. It is found that the coumarin 6 rotates slower in n-decane than in methanol especially at higher values of viscosity over temperature. Two methods are chosen to determine the ground state and excited state dipole moments. The change in dipole moments is estimated from Bakhshiev-Chamma-Viallet equations and, the ground and excited state dipole moments from Kawski et al. equations, by using the variations of the Stokes shifts with the dielectric constant and refractive index of the solvent. Our results are quite reliable which are solvatochromic correlation obtained using solvent polarity functions. The reported results show that excited state dipole moment is greater than ground state dipole moment, which indicates that the excited state is more polar than the ground state.     

Ground and excited state dipole moments of coumarin 337 laser dye

This paper reports that the effects of spectral properties of coumarin 337 laser dye have been investigated in different solvents considering solvent parameters like dielectric constant (?) and refractive index (n) of different solvent polarities. The ground state (μ_g) and excited state (μ_e) dipole moments are calculated using Lippert's, Bakhshiev's, and Kawski-Chamma-Viallet's equations. In all these three equations the variation of Stokes shift was used to calculate the excited state (μ_e) dipole moment. It is observed that the Bakhshiev method is comparatively better than the other two methods for ground state and excited state dipole moment calculations. The angle between the excited state and ground state dipole moments is also calculated.     

Influence of strain on built-in dipole moment in asymmetric In x Ga1−x As quantum dot molecules

Strain effects on a built-in electron-hole dipole moment are investigated in asymmetric In _x Ga_1?x As coupled quantum dots. We compute electron-hole separation as a function of alloy compositions for both electron and hole resonance cases. It is noted that the inclusion of strain enhances the built-in dipole moments and that the inverted electron-hole alignment is found for electron and hole resonances. Furthermore, the reversal of dipole moments gives rise to different asymmetric Stark shifts in each transition spectrum.     

Influence of fluorination and chain length on the static dielectric properties of nematogenic bi-cyclohexyl phenyl derivatives

Effects of fluorination and chain length of six bi-cyclohexyl phenyl compounds (3ccp-f, 3ccp-ff, 3ccp-fff, 5ccp-f, 5ccp-ff, 5ccp-fff) on their physical properties have been investigated. All the compounds exhibit nematic phase over a wide range of temperatures. Molecular mechanics calculation reveals that dipole moments of the molecules increases (1.93D to 3.37D) with fluorination in both propyl- and pentyl-based systems; increment in f to ff derivatives is more than in ff to fff derivatives. However, no change in dipole moment is observed with increased chain length. In the nematic phase, average value of dielectric constant (?_avg) is less than the extrapolated values of ?_iso in isotropic phase. Increased fluorination also decreases splay elastic constant, and thus faster response is expected in triply fluorinated compounds.     

Spectroscopic Studies of Fluorenone Derivatives

The absorption and steady-state fluorescence spectra of fluorenone, 1-hydroxyfluorenone, and 3-dimethylaminofluorenone have been obtained for various concentrations in a series of non-polar and polar solvents. The substituents (-OH and -N(CH₃)₂) as the electron-donating functional groups cause a large shift of the longwave absorption band and Stokes' shift of the monomer- and excimer-fluorescence bands in comparison with fluorenone. The total emission spectrum of 3-dimethylaminoflourenone in polar aprotic solvents exhibits a new band at 500 nm originating form the emission of the twisted intramolecular charge transfer (TICT) isomer. The excited state dipole moments of the emiting species of the molecule studied are determined using the solvatation shift method and calculated values of the ground state dipole moments.     

Femtosecond laser control of intramolecular vibrations in a liquid

Optical control of coherent intramolecular oscillations in chloroform CHCl₃ and dimethyl sulfoxide (CH₃)₂SO is attained experimentally under normal conditions by means of femtosecond polarization spectroscopy. Nonresonant excitation of the medium is accomplished by a sequence of two linearly polarized laser pulses. The state of the medium is probed by the third pulse via the optical Kerr effect. We show that control over the vibrational dynamics of molecules on a sub-picosecond scale can be achieved by varying the delay between the excitation pulses and their relative intensity.     

FTIR spectroscopic studies of the matrix photoionization and photolysis products of methylene halides

Matrix photoionization of methylene bromide produced absorptions at 1019, 897, and 788 cm^?1 identified previously as CBr₂⁺, CHBr₂⁺, and CHBr₂. High-resolution FTIR spectra revealed overlapping 1/2/1 triplets for natural bromine isotopes with individual linewidths near 0.2 cm^?1. New absorptions at 3121, 2897, and 1345 cm^?1 are assigned to the (CH₂Br⁺)Br cation complex which yields CHBr₂⁺ on photolysis. A substantially increased yield of the CHCl₂⁺ species made possible observation of the CH stretching mode at 3033 cm^?1 and the symmetric CCl₂ stretching mode at 845 cm^?1 along with the previously observed stronger 1291- and 1044-cm^?1 fundamentals. The high resolution and enhanced signal-to-noise capability of the FTIR are clearly demonstrated in this investigation.