Intermolecular vibrational modes and orientational dynamics of cooperative hydrogen-bonding dimer of 7-azaindole in solution

We observed the low-frequency Raman-active intermolecular vibrational modes of 7-azaindole in CCl(4) by femtosecond Raman-induced Kerr effect spectroscopy. To understand the dynamical aspects and vibrational modes of 7-azaindole in the solution, the ultrafast dynamics of 1-benzofuran in CCl(4) was also examined as a reference and ab initio quantum chemistry calculations were performed for 7-azaindole and 1-benzofuran. The cooperative hydrogen-bonding vibrational bands of 7-azaindole dimer in CCl(4) appeared at 89 cm(-1) and 105 cm(-1) represent the overlap of stagger and wheeling modes and the intermolecular stretching mode, respectively. They are almost independent of the concentration in the solution. We further found from the low-frequency differential Kerr spectra of the solutions with neat CCl(4) that the intermolecular motion in the low frequency region below 20 cm(-1) was less active in the case of 7-azaindole/CCl(4) than in the case of 1-benzofuran/CCl(4). The slow orientational relaxation time in 7-azaindole/CCl(4) is ~3.5 times that in 1-benzofuran/CCl(4) because of the nature of the dimerization of 7-azaindole.     

Intermolecular vibrations and diffusive orientational dynamics of Cs condensed ring aromatic molecular liquids

The ultrafast dynamics, including the intermolecular vibrations and the diffusive orientational dynamics, of the neat C(s) symmetry condensed ring aromatic molecular liquids benzofuran, 1-fluoronaphtalene, and quinoline were investigated for the first time by means of femtosecond Raman-induced Kerr effect spectroscopy. To understand the features of these C(s) condensed ring aromatic molecular liquids, reference singular aromatic molecular liquids, furan, fluorobenzene, pyridine, and benzene, were also studied. High quality low-frequency Kerr spectra of the aromatic molecular liquids were obtained by Fourier-transform deconvolution analysis of the measured Kerr transients. The Kerr spectra of the C(s) condensed ring aromatic molecular liquids are bimodal, as are those of the reference singular aromatic molecular liquids. The first moment of the intermolecular vibrational spectrum and the peak frequencies of the high- and low-frequency components in the broad spectrum band were compared with their molecular properties such as the rotational constants, molecular weight, and intermolecular (bimolecular) force. The comparisons show that the molecular volume (related to molecular weight and rotational constants) is a dominant property for the characteristic frequency of the entire intermolecular vibrational spectrum. The observed intramolecular vibrational modes in the Kerr spectra of the aromatic molecular liquids were also assigned on the basis of the ab initio quantum chemical calculation results. In their picosecond diffusive orientational dynamics, the slowest relaxation time constant for both the condensed ring and singular aromatic molecular liquids can be accounted for by the simple Stokes-Einstein-Debye hydrodynamic model.     

Low-frequency modes of the benzoic acid dimer in chloroform observed by the optical Kerr effect

The low frequency Raman spectral density associated with the intermolecular hydrogen-bonding interaction of benzoic acid in chloroform was investigated through the ultrafast optically-heterodyne-detected optical Kerr effect. The low-frequency solute Raman spectrum was obtained by Fourier transform analysis and subtraction of the solvent spectrum from the solution spectrum. The resulting difference spectrum has a broad band below 150 cm(-1) with a peak at around 80 cm(-1). Previous studies of aromatic liquids suggest that the origin of such a low-frequency band is librational motion, although intermolecular hydrogen-bonding modes in benzoic acid may also contribute. To clarify these contributions to the low-frequency band, methyl benzoate was used to estimate the librational component; its structure is similar to benzoic acid, but it forms no intermolecular hydrogen bonds. Both librational and intermolecular modes were found to contribute to the low-frequency Raman spectrum of the dimer and thus can be separated. These experimental results were compared with the results of density functional theory calculations. In addition, the effect of deuteration on the Raman spectrum was also investigated.     

Hydrogen-bonding dynamics in aqueous solutions of amides and acids: monomer, dimer, trimer, and polymer

Hydrogen-bonding dynamics in aqueous solutions of series of amides and acids have been investigated by means of femtosecond Raman-induced Kerr effect spectroscopy and ab initio quantum chemistry calculation. The amides and acids studied here are acetamide, 1,3-propanedicarboxamide, 1,3,5-pentanetricaroxamide, polyacrylamide with Mw=1500, acetic acid, 1,3-propanedicarboxylic acid, 1,3,5-pentanetricarboxylic acid, and poly(acrylic acid) with Mw=2000. The femtosecond damped transient feature for aqueous amide solutions, which arises from the intermolecular hydrogen bonds of amide and water, becomes clearer with the larger molecular weight of amide. A characteristic vibrational band at about 100 cm(-1) is assigned as the hydrogen-bonding vibrational mode and the ab initio quantum chemistry calculation result indicates that at least two waters, which make up the hydrogen-bonding network with amide, are necessary for this mode. The hydrogen-bonding vibrational mode at about 100 cm(-1) in aqueous amide solutions shifts to the higher frequency with the larger molecular weight amide in consequence of the stronger intermolecular interaction between amide and water. The evidence likely comes from the stronger hydrophobic interaction for polymer than oligomers and monomer. In the picosecond time region, an extra slow relaxation process with a time constant of about 60 ps has been found in the aqueous polymer solutions. The relaxation is assigned as a local motion of the constitutional repeat unit of polymers from comparison with monomer and oligomers.     

Ultrafast dynamics in aqueous polyacrylamide solutions.

We have investigated the ultrafast dynamics of aqueous polyacrylamide ([-CH(2)CH(CONH(2))-](n), or PAAm) solutions using femtosecond optical heterodyne-detected Raman-induced Kerr effect spectroscopy (OHD-RIKES). The observed aqueous PAAm dynamics are nearly identical for both M(w) = 1500 and 10 000. Aqueous propionamide (CH(3)CH(2)CONH(2), or PrAm) solutions were also studied, because PrAm is an exact model for the PAAm constitutional repeat unit (CRU). The longest time scale dynamics observed for both aqueous PAAm and PrAm solutions occur in the 4-10 ps range. Over the range of concentrations from 0 to 40 wt %, the picosecond reorientation time constants for the aqueous PAAm and PrAm solutions scale linearly with the solution concentration, despite the fact that the solution shear viscosities vary exponentially from 1 to 264 cP. For a given value of solution concentration in weight percent, constant ratios of measured reorientation time constants for PAAm to PrAm are obtained. This ratio of PAAm to PrAm reorientation time constants is equal to the ratio of the volume for the PAAm constitutional repeat unit (-CH(2)CHCONH(2)-) to the molecular volume of PrAm. For these reasons, we assign the polymer reorientation dynamics to motions of the entire constitutional repeat unit, not only side group motions. Simple molecular dynamics simulations of H[-CH(2)CH(CONH(2))-](7)H in a periodic box with 180 water molecules support this assignment. Amide-amide and amide-water hydrogen-bonding interactions lead to strongly oscillatory femtosecond dynamics in the Kerr transients, peaking at 80, 410, and 750 fs.     

Intra- and intermolecular electronic relaxation of the second excited singlet and the lowest excited triplet states of 1,3-dimethyl-4-thiouracil in solution

Intramolecular processes of deactivation of 1,3-dimethyl-4-thiouracil (DMTU) from the second excited singlet (S2) (pi, pi*) and the lowest excited triplet (T1) (pi, pi*) states have been studied using perfluoro-1,3-dimethylcyclohexane (PFDMCH) as a solvent. The spectral and photophysical (PP) properties of DMTU in CCl4, hexane and water have also been described. For the first time, the fluorescence from S2 state DMTU has been observed. The picosecond lifetime of DMTU in the S2 state (tau(S2)) in PFDMCH has been proposed to be determined by a very fast intramolecular reversible process of hydrogen abstraction from the ortho methyl group by the thiocarbonyl group. The shortening of tau(S2) in CCl4 is interpreted to be caused by the intermolecular interactions between DMTU (S2) and the solvent. Results of the phosphorescence decay as a function of DMTU concentration were analyzed using the Stern-Volmer formalism, which enabled determination of the intrinsic lifetime of the T1 state (tau0(T1)) and rate constants of self-quenching (k(sq)). The lifetimes, tau0(T1), of DMTU in PFDMCH and CCl4 are much longer than the values hitherto obtained in more reactive solvents. The PP properties of DMTU both in the S2 and T1 states have been shown to be determined by the thiocarbonyl group.     

Intermolecular vibrational mode of the benzoic acid dimer in solution observed by terahertz time-domain spectroscopy

The low-frequency modes of the benzoic acid (BA) dimer and its analogues in carbon tetrachloride (CCl(4)) have been investigated by terahertz time-domain spectroscopy. The solute spectrum is obtained by subtracting the solvent contribution from that of the solution. The difference spectrum of BA in CCl(4) has a broad band with a peak at 68 cm(-1). To assign the observed band, the spectrum is compared with spectra of other aromatic molecules, such as benzene and phenol in addition to p-methyl BA and deuterated BA species (BA-d(OH) and BA-d(5)) in CCl(4). The band at 68 cm(-1) is assigned to the cogwheel mode of the BA dimer. Density functional theory calculations also support this assignment. Finally, spectral lineshape analysis based on the multimode Brownian oscillator model is applied to the THz spectra for all the samples.     

Interplay of H‐Bonds with Aromatics in Isolated Complexes Identifies Isomeric Carbohydrates

The tremendous isomeric diversity of carbohydrates enables a wide range of their biological functions but makes the identification and study of these molecules difficult. We investigated the ability of intermolecular interactions to communicate structural specificity of carbohydrates to protonated aromatic molecules in non‐covalent complexes, isolated and cooled in the gas phase. Our study revealed that small structural differences between carbohydrate isomers of any type, including enantiomers, are accurately communicated by these interactions to aromatic molecules as detectable changes in their electronic excitation spectra. The specific response of the aromatics to the isomers of carbohydrates is fine‐tuned by the interplay of the various involved non‐covalent bonds. These findings enable the gas‐phase identification and relative quantification of any isomers of oligosaccharides in their solution mixtures using the 2D UV‐MS fingerprinting technique.     

Wave function delocalization and large-amplitude vibrations of helium on corrugated aromatic microsurfaces: tetracene.He and pentacene.He van der Waals complexes

We report accurate quantum three-dimensional calculations of highly excited intermolecular vibrational states of the van der Waals (vdW) complexes tetracene.He and pentacene.He in the S1 excited electronic state. The aromatic molecules were taken to be rigid and the intermolecular potential energy surfaces (IPESs) were modeled as a sum of atom-atom Lennard-Jones pair potentials. The IPESs are corrugated in the direction of the long (x) axis of the aromatic molecules, due to the presence of the symmetrically equivalent global double minimum for tetracene.He, and a triple minimum (central global minimum and two equivalent local minima) for pentacene.He, on each side of the aromatic plane. Both IPESs have two additional minor equivalent local minima further away from the center of the molecule. The vdW vibrational states analyzed in this work cover about 80% of the well depths of the IPESs. The mode coupling is generally weak for those states whose out-of-plane (z) mode is unexcited. However, the z-mode fundamental is strongly coupled to the short-axis (y) in-plane mode, so that the pure z-mode excitation could not be identified. The He atom exhibits large in-plane spatial delocalizaton already in the ground vdW vibrational state, which increases rapidly upon the excitation of the in-plane x and y modes, with little hindrance by the corrugation of the aromatic microsurfaces. For the vdW vibrational energies considered, the He atom spatial delocalization reaches Deltax and Deltay values of approximately 5 and 4 A, respectively, and is limited only by the finite size of the aromatic substrates. Side-crossing delocalization of the wave functions on both sides of the molecular plane is found at excitation energies >30 cm(-1), giving rise to the energy splittings of the pairs of states symmetric/antisymmetric with respect to the aromatic plane; the splittings show strong vdW vibrational mode specificity.     

Relaxation of the optical Kerr effect of anisotropic molecules in mixed liquids

The relaxation time of the Kerr effect of nitrobenzene and m-nitrotoluene in various mixtures with carbon tetrachloride and various alcohols was determined by measuring the kinetics of the Kerr effect using picosecond laser techniques. These measurements yield information on the rotational motion of molecules in liquids. The relaxation time data are interpreted in terms of an effective local viscosity effect, pair correlation, and coupling of rotational motion with shear modes.     

Determination of absolute photoionization cross‐sections of aromatics and aromatic derivatives

The absolute photoionization cross‐sections of aromatics and aromatic derivatives including toluene, ethylbenzene, n‐propylbenzene, o‐xylene, m‐xylene, p‐xylene, 1,3,5‐trimethylbenzene, styrene, phenylacetylene, indene, indane, 1‐methylnaphthalene, benzyl alcohol and benzaldehyde were measured at the photon energy range from ionization thresholds to 11.7 eV. The experiments were performed by tunable synchrotron vacuum ultraviolet (VUV) photoionization mass spectrometry. Benzene was chosen as a calibration standard, since its photoionization cross‐section is well known. Binary liquid mixtures of the investigated molecules and benzene were used in the measurements. Photo‐induced fragments from the molecules were also observed, and their photoionization cross‐sections are also presented. Copyright © 2009 John Wiley & Sons, Ltd.     

Synthesis of Cumene from Lignin by Catalytic Transformation

Cumene is an important intermediate and chemical in chemical industry.In this work,directional preparation of cumene using lignin was achieved by a three-step cascade process.The mixture aromatics were first produced by the catalytic pyrolysis of lignin at 450℃ over 1% Zn/HZSM-5 catalyst,monocyclic aromatics with the selectivity of 85.7 wt% were obtained.Then,the catalytic dealkylation of heavier aromatics resulted in benzene-rich aromatics with 93.6 wt% benzene at 600℃ over Hβ catalyst.Finally,the cumene synthesis was performed by the aromatic alkylation,giving cumene selectivity of 91.6 C-mol% using the[bmim]Cl-2AlCl₁₃ ionic liquid at room temperature for 15 min.Besides,adding a small amount of methanol to the feed can efficiently suppress the coke yield and enhance the aromatics yield.The proposed transformation potentially provides a useful route for production of cumene using renewable lignin.     

聚苯乙烯热降解机理的理论研究

采用密度泛函理论B3LYP/6-311G（d）方法,对聚苯乙烯（PS）热降解反应机理进行了研究。PS热降解的主要产物是苯乙烯,其次是甲苯、α-甲基苯乙烯、乙苯和二聚体等芳烃化合物。PS热降解反应主要包括主链C-C键均裂、β-断裂、氢转移和自由基终止等反应。针对以上各类反应进行了路径设计和理论计算分析,对参与反应的分子的几何结构进行了优化和频率计算,获得了各热降解路径的标准动力学和热力学参数。计算结果表明,苯乙烯主要由自由基的链端β-断裂反应形成;二聚体主要由分子内1,3氢转移的反应形成;α-甲基苯乙烯由分子内的1,2氢转移后进行β-断裂形成;甲苯由苯甲基自由基夺取主链上的氢原子形成;乙苯由苯乙基自由基夺取氢原子形成。动力学分析表明,苯乙烯形成所需要的能垒低于其他产物形成所需要的能垒,故苯乙烯为主要的热降解产物;这与相关实验结果基本一致。     

Temperature Dependence of Kerr Coefficient of Binary Liquid Mixtures of Aprotic-Aprotic Molecules

Abstract

The electro optical Kerr coefficients of binary liquid mixtures, comprising of aprotic-aprotic molecules only, are measured over the temperature range of 286 K to 315 K. To with in experimental errors, the logarithm of Kerr coefficient can be expressed as Van't Hoff type expression to the reciprocal of temperature. Information on the interaction energy between the constituents of the binary mixtures is thereby obtained. It is found that the interaction energy in aromatic ketone-aliphatic nitrile binary mixtures is comparatively higher than in the binary mixtures with aliphatic ketone-aliphatic nitriles, aromatic ketone-aromatic nitrile and aromatic ketone-aliphatic ketones components. This is attributed to the dipole-dipole interaction existing between the components of the binary mixtures.     

Accidental vibrational degeneracy in vibrational excited states observed with ultrafast two-dimensional IR vibrational echo spectroscopy

The coupling between the OD stretch v=2 level and benzene-ring modes in 2-methoxyphenol-OD (hydroxyl H replaced by D) is observed with ultrafast two-dimensional (2D) IR vibrational echo spectroscopy. Because of this coupling, the 1-2 transition peak in the 2D spectrum is split into a doublet with peaks of approximately equal amplitudes. Several molecules and solvents were used to study this phenomenon. Near-IR (NIR) spectroscopy measurements and density-functional theory calculations (B3LYP6-31+G(d,p) level) were also applied. Experimental results and calculations show that the OD stretch 1-2 transition is coupled to a combination band related to the benzene-ring motions. A simple quantum-mechanical model indicates that the combination band has a frequency of 5172 and 5176.5 cm(-1) in CCl4 and hexane, respectively. The transition between this combination band and the ground state is too weak to detect by NIR. The transition between this band and the OD stretch first excited state is also so weak that most of the intensity of the doublet comes from the oscillator strength produced by coupling to the OD stretch. The model gives the coupling strengths as 6.5 and 7 cm(-1) in CCl4 and hexane, respectively.     

Ultrafast Time‐Resolved Transient Structures of Solids and Liquids by Means of Extended X‐ray Absorption Fine Structure

Detection of ultrafast transient structures and the evolution of ultrafast structural intermediates during the course of reactions has been a long standing goal of chemists and biologists. This article will be restricted to nanosecond, picosecond and shorter time‐resolved extended X‐ray absorption fine structure (EXAFS) studies, its aim being to present the progress and problems encounter in measurements and understanding the structure of transients. The recent advances in source technology has stimulated a wide variety of novel experiments using both synchrotrons and smaller laboratory size systems. With more efficient X‐ray lenses and detectors many of the previously difficult experiments to perform, because of the exposure time required and weak signals, will now be easily performed. The experimental system for the detection of ultrafast time‐resolved EXAFS spectra of molecules in liquids is described and the method for the analysis of EXAFS spectra to yield transient structures is given. We believe that utilizing our table‐top ultrafast X‐ray source and the polycapillary optics in conjunction with dispersive spectrometer and charge coupled devices (CCD) we will be able to determine the structure of many reaction intermediates and excited states of chemical and biological molecules in solid and liquid state.     

Concentration-dependent frequency shifts and Raman spectroscopic noncoincidence effect of the C=O stretching mode in dipolar mixtures of acetone/dimethyl sulfoxide. Experimental, theoretical, and simulation results

The nu(C=O) Raman band frequencies of acetone have been analyzed to separate the contributions of the environmental effect and the vibrational coupling to the gas-to-liquid frequency shifts of this band and to elucidate the changes in these two contributions upon dilution in DMSO. We have measured the frequencies of the nu((12)C=O) band in acetone/DMSO binary mixtures, the nu((13)C=O) band of the acetone-(13)C=O present as a natural abundance isotopic impurity in these mixtures, and both the nu((12)C=O) and nu((13)C=O) bands in the acetone-(12)C=O/acetone-(13)C=O isotopic mixtures at infinite dilution. These frequencies are compared with those of the nu((12)C=O) band in the acetone/CCl(4) binary mixtures measured previously. We have found the following three points: (i) The negative environmental contribution for the nu((12)C=O) oscillator of acetone completely surrounded by DMSO is reduced in magnitude by +5.5 cm(-1) and +7.8 cm(-1) upon the complete substitution of DMSO with acetone and CCl(4) molecules, respectively, indicating the progressive reduction of the attractive forces exerted by the environment on the nu((12)C=O) mode of acetone. (ii) In DMSO and other solvents, the contribution of the vibrational coupling to the frequency of the isotropic Raman nu((12)C=O) band of acetone becomes progressively more negative with increasing acetone concentration up to a value of -5.5 cm(-1), while the contribution to the frequency of the anisotropic Raman band remains approximately unchanged. The only difference resides in the curvatures of the concentration dependencies of these contributions which depend on the relative solute/solvent polarity. (iii) The noncoincidence effect (separation between the anisotropic and isotropic Raman band frequencies) of the nu(C=O) mode in the acetone/DMSO mixtures exhibits a downward (concave) curvature, in contrast to that in the acetone/CCl(4) mixtures, which shows an upward (convex) curvature. This result is supported by MD simulations and by theoretical predictions and is interpreted as arising from the reduction and enhancement of the short-range orientational order of acetone in the acetone/DMSO and acetone/CCl(4) mixtures, respectively.     

Molecular dynamics investigation with the time resolved optical Kerr effect on the CS2-C6H6 mixtures

An investigation of the molecular dynamics in pure liquids and in mixtures through the technique of time resolved optical Kerr effect is performed. The samples studied were the mixtures of carbon disulfide (CS(2)) with benzene (C(6)H(6)). The molecular dynamics of the pure liquids is briefly discussed while the main results are obtained for the mixtures. A slow dynamics component is observed for the optical heterodyne detected optical Kerr effect transient decaying exponentially with time constants on picosecond time scale. The fast subpicosend time relaxations are analyzed in terms of the nondiffusive component of the spectral response that is associated with the molecular dynamics. The modifications of the spectrum are quantified, and the explanation of the observed changes is given in terms of the structural interaction configurations that produced changes in the intermolecular potential within which the molecules execute librational motions.     

Volumetric behaviour of binary liquid mixtures of dimethylsulphoxide with substituted benzenes at 303.15 k

Excess molar volumes (V ^E ) for binary mixtures of dimethyl sulphoxide (DMSO) with substituted benzenes have been measured at 303.15?K. The substituted benzenes include toluene, ethylbenzene, chlorobenzene, bromobenzene and nitrobenzene. The measured V ^E data is positive for the mixtures of DMSO with nitrobenzene and is completely negative over the entire composition range in the mixtures of toluene, ethylbenzene and chlorobenzene and an inversion in sign is observed in the bromobenzene system. The experimental results are analysed in terms of intermolecular interactions and effect of substitutents on benzene ring between unlike molecules.     

Determination of benzene, toluene, ethylbenzene and xylene in river water by solid-phase extraction and gas chromatography.

A rapid and reproducible method is described that employs solid-phase extraction (SPE) using dichloromethane, followed by gas chromatography (GC) with flame ionization detection for the determination of benzene, toluene, ethylbenzene, xylene and cumene (BTEXC) from Buriganga River water of Bangladesh. The method was applied to detect BTEXC in a sample collected from the surface, or 5 cm depth of water. Two-hundred milliliters of n-hexane-pretreated and filtered water samples were applied directly to a C18 SPE column. BTEXC were extracted with dichloromethane and the BTEX concentrations were obtained to be 0.1 to 0.37 microg ml(-1). The highest concentration of benzene was found as 0.37 microg ml(-1) with a relative standard deviation (RSD) of 6.2%; cumene was not detected. The factors influencing SPE e.g., adsorbent types, sample load volume, eluting solvent, headspace and temperatures, were investigated. A cartridge containing a C18 adsorbent and using dichloromethane gave a better performance for the extraction of BTEXC from water. Average recoveries exceeding 90% could be achieved for cumene at 4 degrees C with a 2.7% RSD.