Gas‐phase structure and new vibrational study of methyl trifluoroacetate (CF3C(O)OCH3)

The molecular structure of methyl trifluoroacetate (CF₃C(O)OCH₃) has been determined in the gas phase from electron‐diffraction data supplemented by ab initio (MP2) and DFT calculations using different basis sets. Experimental data revealed an anti conformation with a dihedral angle θ (CCOC) = 180°. Quantum mechanical calculations indicate the possible existence of two conformers, differing by a rotation about the C(O) O bond. The global minimum represents a C_s‐symmetric structure in which the CF₃ group has the anti orientation with respect to the CH₃ group, but there is another potential minimum, much higher in energy, representing a C_s‐symmetric structure with a cis conformation. The preference for the anti conformation was studied using the total energy scheme and the natural bond orbital (NBO) partition scheme. Additionally, the total potential energy has been deconvoluted using a six‐fold decomposition in terms of a Fourier‐type expansion, showing that the electrostatic and steric contributions are dominant in stabilizing the anti conformer. Infrared spectra of CF₃C(O)OCH₃ were obtained for the gaseous and liquid phases, while the Raman spectrum was recorded for the liquid phase. Harmonic vibrational frequencies and a scaled force field have been calculated, leading to a final root mean‐square deviation of 9 cm⁻¹ when comparing experimental and calculated frequencies. Copyright © 2009 John Wiley & Sons, Ltd.     

Raman study of temperature and pressure effects on vibrational relaxation in liquid CHCl3 and CDCl3

The Raman line shapes of the ν₁(A ₁)C-H and C-D stretching fundamentals in liquid CHCl₃ and CDCl₃ have been measured as a function of pressure from 1 bar to 4·5 kbar within the temperature range 30°C to 90°C. Densities have also been determined under the same experimental conditions. The vibrational relaxation rates are obtained from the isotropic component of the Raman band and the experimental results can be summarized as follows: (i) as T increases at constant density the vibrational relaxation rate increases; (ii) at constant T, the increase in density produces an increase in the relaxation rate; (iii) an increase in temperature at constant pressure results in an increased relaxation rate. The above three cases hold for the CDCl₃ liquid, whereas only (ii) may be stated for the CHCl₃ liquid.

The experimental vibrational data are interpreted in terms of the Kubo stochastic line-shape theory and the collinear-isolated-binary-collision model proposed by Fischer and Laubereau. Application of the Kubo formalism shows that vibrational dephasing is the dominant relaxation mechanism and that the modulation is fast both in liquid CHCl₃ and CDCl₃.

Interpretation in terms of the binary collision dephasing model leads to the following results: (i) the pure dephasing mechanism seems to be the dominant broadening mechanism for the isotropic Raman line shapes studied; (ii) the calculated dephasing rates as a function of density and temperature show agreement with the experimental data. In these calculations the elastic collision times are obtained from the modified Enskog theory.     

The absorption and magnetic circular dichroism of spectra of Cs2NaPrCl6

The room temperature absorption and magnetic circular dichroism spectra and the absorption spectrum at liquid helium (liquid He) temperature have been measured for Cs₂NaPrCl₆. At room temperature the crystal is cubic and the Pr³⁺ sites have O _h symmetry. All terms above 15 000 cm^-1, except ¹S₀, have been assigned and a previous assignment in PrCl₆ ^3- has been shown to be incorrect. The transition at 20 631 cm^-1 is assigned to ³H₄(A _1g ) →³P₁(T _1g ), in contradiction to previous assignments of Pr³⁺ spectra in other systems. A rich vibrational structure was observed in every transition. Vibrations have been assigned using the site group approximation and there is substantial agreement with the vibrational assignments in Cs₂NaEuCl₆. A crystal phase transition takes place between room temperature and liquid nitrogen temperature and the O _h forbidden transitions, A _1g →E_g and T _2g , are observed. At lower temperatures many additional lines are observed but it is unclear presently whether they are due to lower symmetry or a breakdown of the site group approximation.     

Normal co-ordinate analysis of 1, 8-dibromooctane

The organic compound 1,8-dibromooctane (1,8-DBO) exists in liquid phase at ambient temperatures and has versatile synthetic applications. In its liquid phase 1,8-DBO has been expected to exist in four most probable conformations, with all its carbon atoms in the same plane, having symmetries C _2h , C _i , C ₂ and C ₁ . In the present study a detailed vibrational analysis in terms of assignment of Fourier transform infrared (FT-IR) and Raman bands of this molecule using normal co-ordinate calculations has been done. A systematic set of symmetry co-ordinates has been constructed for this molecule and normal co-ordinate analysis is carried out using the computer program MOLVIB. The force-field transferred from already studied lower chain bromo-alkanes is subjected to refinement so as to fit the observed infrared and Raman frequencies with those of calculated ones. The potential energy distribution (PED) has also been calculated for each mode of vibration of the molecule for the assumed conformations.     

Primary isotopic effect on the magnetic shielding of tin nuclei (117Sn and 119Sn)

The Kirkwood-Buff statistical mechanical theory of surface tension γ for monatomic fluids is extended to molecular fluids. A rigorous expression for γ is derived in terms of the angular pair distribution function f(z ₁ R ₁₂θ₁θ₂) of an equilibrium fluid-fluid system (liquid-gas, liquid-liquid, or gas-gas). The Fowler approximation is applied for the liquid-gas case, and a simple expression for γ is derived in terms of the bulk liquid angular pair correlation function g(R ₁₂θ₁θ₂). Thermodynamic perturbation theory for g(R ₁₂θ₁θ₂) is also used to calculate γ theoretically. The theoretical results are compared with experimental values.     

Simulation study of solvent shifts of vibrational overtone spectra

Buckingham's theory of the solvent shift of vibrational spectral frequencies predicts that the shift of the v = 0 → n overtone transition is n times the shift of the fundamental v = 0 → 1. We test this prediction by molecular dynamics simulations using existing intermolecular potential models for liquid N₂ and dilute N₂ in liquid Ar, at standard state conditions. We extend Buckingham's theory by including additional intramolecular potential and perturbation terms which lead to solvent-induced anharmonicity, i.e. O(n ²) terms in the solvent shift. The simulations show that Buckingham's prediction is not accurate for N₂ at standard liquid state conditions. We find that at these conditions there is a significant positive O(n ²) contribution to the solvent shifts and that for n ～ 20 the shifts change sign from red to blue. Simulation results and indirect evidence from shock wave experiments with liquid N₂ show that Buckingham's prediction is more accurate for high-pressure high-temperature conditions, where the shifts are blue and only slightly nonlinear in n.     

Enhancement of optical nonlinearity in a guest-host system by nematic ordering

Second-harmonic generation (SHG) has been studied for understanding the enhancement mechanism for the second-order optical nonlinearity by the nematic (or axial) ordering in a liquid crystal doped with one-dimensional nonlinear optical (NLO) organic molecules. An extended version of the Maier-Saupe mean-field theory for nematic liquid crystals was developed to obtain analytical expressions for the second-order NLO coefficients in terms of the axial order, the polar order and the effective nematic potential. From the SHG data in a guest-host system composed ofN,N'-dimethylaminonitrostilbene molecules (0.5% by weight) and a liquid crystal, the enhancement of the second-order NLO coefficient,d ₃₃, by nematic ordering becomes almost 3, which agrees well with our theoretical predictions.     

Molecular dynamics of liquids modelled by ‘2-Lennard-Jones centres’ pair potentials

The molecular dynamics study based on two-Lennard-Jones (12-6) centres pair potentials, with reduced bond lengths in the range 0·5 ?l/σ?0[sbreve]d8, and with ε, σ-parameters simulating liquid F₂, Cl₂, Br₂ and CO₂ (14) is extended to time correlation functions. The calculated properties include: translational velocity and force self correlation functions; orientational self-correlation functions <P _1,2(Î . Î(t))>, a cross correlation function for P ₂, angular momentum (J), and torque self-correlation functions. Diffusion constants (D) and rotational relaxation times (τ₁, τ₂, τ _J ) have been evaluated and where possible compared with experimental data (D and τ _J for F₂, τ₂ for Cl₂). Calculations with 108 or 256 molecules are reported for several densities and temperatures for four model liquids. The nature of the one-particle motion is analysed qualitatively in terms of quasi-oscillations and -librations. It is difficult to fit the observed features into the framework of physical models proposed in the literature. The parametrization in terms of memory functions will be reported in a subsequent paper.     

Thermodynamic and structural properties of liquids modelled by ‘2-Lennard-Jones centres’ pair potentials

Molecular dynamics calculations have been carried out for model liquid systems of N (=108 or 256) molecules interacting through two Lennard-Jones (12–6) centres coinciding with the positions of the atomic masses (the ‘atom-atom’ pair potential). The objectives were (a) to study the dependence of the properties on the molecular anisotropy defined by the reduced distance l*=l/σ between the centres in the range 0·5–0·8; and (b) to compare the computed quantities with those of real liquids (F₂, Cl₂, Br₂, CO₂). This paper deals with thermodynamic and structural features. Time-dependent correlations will be treated in a future communication.

In the liquid region not too far from the triple point the energy and pressure isochores are well represented by straight lines, the slopes of which increase with density and anisotropy. Thermodynamically consistent expressions for the energy and pressure as functions of density and temperature have been obtained for each system.

With Lennard-Jones parameters adjusted so as to secure the best overall fit, the agreement between experimental and computed thermodynamic properties is very satisfactory for F₂ (l*=0·505), quite good for Cl₂ and Br₂ (l*=0·608–0·63), but rather poor for CO₂ (l*=0·793). The ‘interatomic distances’ are close to the experimental values.

The static structural correlations are discussed in terms of the pair-correlation functions (pcf) g _A(r*) for the separation between ‘atoms’, the first few functions g_ll'm (R*) which arise from the expansion of the g(R*, θ₁, θ₂, φ₁₂) in spherical harmonics, and the pcf's for certain special near-neighbour configurations. The computed atom-atom structure factor is compared with the experimental data for liquid Br₂.

Mean square forces and torques have been evaluated and are related to some experimental results.     

Relation between Tolman length and isothermal compressibility for simple liquids

The Tolman length δ 0 of a liquid with a plane surface has attracted increasing theoretical attention in recent years,but the expression of Tolman length in terms of observable quantities is still not very clear.In 2001,Bartell gave a simple expression of Tolman length δ 0 in terms of isothermal compressibility.However,this expression predicts that Tolman length is always negative,which is contrary to the results of molecular dynamics simulations(MDS) for simple liquids.In this paper,this contradiction is analyzed and the reason for the discrepancy in the sign is found.In addition,we introduce a new expression of Tolman length in terms of isothermal compressibility for simple fluids not near the critical points under some weak restrictions.The Tolman length of simple liquids calculated by using this formula is consistent with that obtained using MDS regarding the sign.     

Mixed hyperfine interactions in Fe-Mg-O: magnetic behaviour

The complex Mössbauer spectra exhibited by Fe_xO (x0.91) and (Fe_1–y Mg _y )_xO (y=0.15–0.85) powder samples at liquid helium temperature have been analysed by a Hamiltonian treatment to allow for the significant electric field gradients present at the Fe²⁺ defect sites. The magnetic behaviour of the defect clusters are considered in terms of antiferromagnetic couplings, consistent with the spin glass-like behaviour reported recently for magnesiowüstite.     

The properties of liquid nitrogen

Measurements are reported of the nitrogen-nucleus spin-lattice relaxation time, T ₁, in liquid nitrogen ¹⁴N₂ and liquid nitrogen ¹⁵N₂ along the liquid-vapour coexistence line from 77·3 K up to the critical temperature and for the fluid at the critical density up to 145 K. Values of the molecular reorientational correlation time, τ _Q , and the molecular angular momentum correlation time, τ _sr , are determined. The values of τ _Q and τ _sr and the relation between them are discussed in terms of various theories of molecular reorientation in molecular liquids. The values of τ _Q and τ _sr are also compared with those predicted by computer simulation methods. It is concluded that the molecular reorientation in liquid nitrogen is not by classical reorientational diffusion except possibly at temperatures near the triple point. It is suggested that at higher temperatures the reorientation is on average by rather large angles and that the process may be quantum mechanical to some extent. (For paper I in this series see reference [8].)     

Vibrational analysis of 1-chlorooctane

The organic compound 1-chlorooctane exists in liquid state at ambient temperatures and has numerous synthetic applications. Fourier transform infrared and Raman spectra of this molecule have been recorded in the range of 4000−400 cm⁻¹ and 3500−200 cm⁻¹, respectively. A detailed vibrational analysis in terms of assignment of the observed frequencies of this molecule for its four most probable conformations in liquid phase, having symmetries C _s and C _l , has been done using normal co-ordinate calculations. The force-field transferred from already studied lower chain chloro-alkanes is subjected to refinement so as to fit the observed infrared and Raman frequencies with those of calculated ones. The potential energy distribution has also been calculated for each mode of vibration of the molecule for the most probable conformations present in its liquid phase.     

Dielectric absorption in mixtures of anisole with some primary alcohols at microwave frequency

Dielectric properties of binary mixtures of anisole with methanol (MeOH), 1-propanol (1-PrOH), 1-butanol (1-BuOH) and 1-heptanol (1-HeOH) over an entire concentration range have been studied at a fixed temperature 40°C. The dielectric constant (ε′) and dielectric loss (ε″) of the binary mixtures of polar liquids have been determined at a microwave frequency of 9.1?GHz. The static dielectric permittivity (ε ₀) of the liquid samples was also determined using a precision LCR meter. Determined values of static dielectric permittivity (ε ₀) and dielectric permittivity (ε*) at 9.1?GHz frequency were used to evaluate relaxation time (τ) and high frequency limit dielectric permittivity (ε _∞). Dielectric parameters were interpreted in terms of molecular interaction between the anisole and alcohol molecules.     

Proton magnetic resonance of ethane in the liquid and gaseous states

The proton chemical shift of ethane is reported, covering for gaseous ethane the density range 0 to 0·5 g cm^-3 and the temperature range 0 to 110°C, and for liquid ethane from the critical temperature down to -55°C. The results are discussed in terms of the van der Waals interaction term σ _w , using a virial expansion including both binary and ternary collisions. A parallel is drawn between the medium shifts and the equation of state for non-ideal gases. Some comments are made regarding (i) the uniqueness of the parameter B for protons in a C-H bond in non-polar molecules, (ii) the neighbour anisotropy contribution σ _a in molecules such as ethane and ethylene, and (iii) the van der Waals gas-to-liquid medium shift, and its temperature dependence, in larger molecules.     

Molecular motions in liquid NOF3

The rotational behaviour of NOF₃ is derived from the band contour analysis of the Raman spectra recorded over the liquid phase. The angular momentum correlation times derived from the J diffusion model show us that this C _3v molecule rotates almost isotropically. The band profiles are interpreted in terms of the rough hard sphere model.     

A unified treatment of the groups SO(4) and SO(3,1)

The irreducible representations of the group SO(4) in which the SO(3) subgroup is reduced are studied by an explicit construction of the operators and the basis in the spinor representation. The basis function which is formally identical with that for the coupling of two angular momentaj ₁ andj ₂ is expressible in terms of a hypergeometric function and strongly resembles the one for the irreducible representations of the groups SO(3,1). For the Lorentz group, the bases for the unitary representations which require unphysical values ofj ₁ andj ₂ are found to be analytic continuation of those for SO(4). The realization of the unitary irreducible representations of the group SO(4) in the Hilbert space of these functions leads, for appropriate unphysical values ofj ₁,j ₂, to the Gelfand-Naimark formula for the principal and complementary series of the representations of SO(3;1). The matrix elements for finite transformations of SO(4) and SO(3,1) can be evaluated, in this approach, in a unified manner by using standard properties of the hypergeometric function. These turn out to be a finite sum of₃ F ₂-functions which, as expected, are polynomials for SO(4) and infinite series for SO(3,1). A number of special matrix elements are calculated from the general formula and these agree with the results obtained previously.The authors are deeply indebted to Professor S.Dutta Majumdar fo many important suggestions and clarifications.     

The vibrational spectra of the cyanide ligand revisited: the ν(CN) infrared and Raman spectroscopy of Prussian blue and its analogues

A careful analysis of the Raman spectra of the M′_x[M(CN)₆]_y Prussian blue species has enabled a general model for the interpretation of the ν(CN) vibrational spectra. The spectral patterns are derived from those of the metal ions with local O_h symmetry. Two limiting models are discussed. A ‘localized mode’ model, involving matrix‐isolated species, is in much better accord with the observations than a ‘factor group’ model. The use of the infrared feature as fingerprint of specific M CN M′ units arises from the axis‐specific nature of individual T_1u modes. The interpretation of the A_1g and E_g Raman features is done in terms of localized vibrations, with involvement of additional energy terms from the lattice motions. Copyright © 2011 John Wiley & Sons, Ltd.     

The vibrational spectrum of crystalline KSCN

The spectrum is reported for the range 700 to 5000 cm^–1; the internal modes of the SCN^– ion are interpreted in terms of the C_s local symmetry group. The combinations of internal and external (lattice) modes are examined in terms of theD _2h factor group. The frequency of the translational mode is found to be 20 cm^–1.I am indebted to Academician A. N. Terenin for direction and encouragement, and to L. A. Gribov and D. S. Bystrov for discussions.     

Liquid–Liquid Transition and Detrapping of Trapped Carriers of P(MMA/BA) Copolymers by Thermally Stimulated Depolarization Current

Poly (methyl methacrylate/butyl acrylate) [P(MMA/BA)] copolymers (M _η～2×10⁵) with different mass percentages of PMMA (100/0, 90/10, 81/19, and 75/25), were synthesized by the method of solution polymerization. In addition to the normal α and ρ peak, a third τ peak is observed in thermally stimulated depolarization current (TSDC) spectra of the copolymers in the high temperature region. The α peak‐corresponds to the glass transition, the ρ peak originates from the detrapping of trapped carriers in the bulk amorphous structure related with flexible side groups, and the τ peak can be attributed to the charge detrapping related to the liquid–liquid transition of the copolymers. The three peaks all move to lower temperature with an increase of the BA component, indicating that the flexible side groups of butyl acrylate not only have an effect of plasticization on the glass transition and liquid–liquid transition, but also make the trap depth shallower and the detrapping process easier for the ρ and τ peaks. The experimental results confirm that TSDC analysis is very sensitive for investigating the liquid–liquid transition of polymers. The liquid–liquid transition temperature (T _LL) of the copolymers follows a type of the Fox equation. Fitting the results gives a T _LL of 102°C for polybutyl acrylate.