Experimental analysis and modified rotor description of the infrared fundamental band of HCl in Ar, Kr, and Xe solutions

We report an experimental study of the rotovibrational fundamental PQR-band shapes in the IR absorption spectra of HCl dissolved in condensed rare gases in a wide range of temperatures. The effective vibrational frequencies are determined from analysis of the fine rotational structure partially resolved in the band wings. The central Q-branch components appear redshifted with respect to the effective vibrational frequencies, their shifts in different solvents found to match the HCl stretching mode shifts in binary Rg...HCl van der Waals heterodimers. Theoretical quasi-free rotor and modified rotor models are applied to describe evolution of the band profiles at changing thermodynamic conditions. Both models are shown to reproduce equally well the observed spectral density distributions in the band wings. However, the modified rotor formalism that accounts for depopulation of the lower-energy rotational solute states provides better agreement with the experiment in the range of the P- and R-branch maxima. We surmise that the Q branches separated from the measured spectral profiles are formed by transitions between rotationally hindered states of diatomic molecules coupled to the solvent by the local anisotropy of the interaction potential.     

Collision-induced absorption of hydrogen deuteride dissolved in liquid neon

First observation of the collision-induced IR-fundamental band of hydrogen deuteride (HD) in liquid neon is described. A developed intracell rattling model yields highly accurate fits to the measured diffuse Q1-branch profiles enabling a detailed shape analysis of the adjacent spectral lines. Strong intracollisional anticorrelation found at the location of the permanent dipole-allowed R1(0) transition is interpreted in the frame of the Fano-Mori theory. A new striking narrowing effect (by 30%) is observed on the sharp Q(q)(1)(0) vibrational line with increasing HD concentration in solutions. The T1(0), U1(0) and a few pair transitions are identified in the spectrum.     

Spectroscopic study of zeolite Na-ETS-10 and ethylene photopolymerization reaction on its surface

Zeolite Na-ETS-10 is studied by the Raman and IR spectroscopy methods. The ethylene polymerization reaction on this zeolite under UV irradiation is studied by IR spectroscopy. It is found that this reaction proceeds at room temperature yielding polyethylene. The experimental data are analyzed using 2D correlation spectroscopy.     

Synthesis of dense ceramics of single-phase mayenite (Ca<Subscript>12</Subscript>Al<Subscript>14</Subscript>O<Subscript>32</Subscript>)O

The nanoporous material mayenite was synthesized by two methods: solid-phase and self-propagating high-temperature (combusting) (SHS) syntheses. The structure of the materials was determined by the X-ray diffraction analysis and IR and Raman spectroscopy.     

Influence of line interference on the vibration-rotation band shapes

The shapes of the CO, v₃, CO₂, and v₃ N₂O fundamental vibration-rotation bands have been studied at various temperatures and in the presence of several perturbing gases. Also the half-widths of CO vibration-rotation lines have been measured at 78 K. In the region of line wings, the measured absorption coefficients deviate from those given by the superposition of Lorentzian profiles. These deviations are explained by the collision-induced line interference that causes redistribution of absorption inside the band. A theory of line mixing is formulated which is based on Markov approximation and on the strong collision model. Simple analytical expressions are obtained for the band shape. The computed shapes are in satisfactory agreement with the experimental results. The deviations from the Lorentz absorption observed in pure CO and in CO-N₂ at low temperature are partially ascribed to the formation of van der Waals dimers.     

Interferometric determination of the dispersion of the vibrational polarizability and the integral intensities of fundamental bands of trifluorochloromethane molecules CF<Subscript>3</Subscript>Cl

Using two-color interferometry, the dispersion of the refraction and the vibrational polarizability of freon molecules CF₃Cl of natural isotopic composition was studied in the lasing range of an IR laser on the basis of the main isotopomer of carbon dioxide (¹²C¹⁶O₂). Simultaneous processing of the data of the absolute refractometric and relative absorption measurements using the Kramers-Kronig formalism made it possible to refine the integral intensities of the fundamental vibrational bands ν₁ and ν₄ and to determine the dispersion of the vibrational polarizability in the range from 1050 to 1250 cm^?1.     

Spectral line parameters in the (4 ← 0) overtone band and the dipole moment function of HI

We present new measurements of the line strengths in the third vibrational overtone band in pure HI and its mixtures with Ne, Ar, and Xe, and report results of the Herman-Wallis analysis for this band. Significance of the higher-order terms in the polynomial representation of the dipole moment function is discussed. It is concluded that the spectroscopic data yield the dipole moment function fully described by a cubic polynomial in powers of the reduced displacement from the equilibrium bond length. In the Padé approximant for the dipole moment function, the vicinity of the saddle point near equilibrium also can be accurately fitted with a cubic polynomial. Pressure line broadening and shifting parameters are reported for mixtures of HI with rare gases.     

Theoretical study of the spectral and structural parameters of van der Waals complexes of the Li+ cation with the H2, D2, and T2 isotopomers of the hydrogen molecule

The three-dimensional vibrational problem for the isolated binary complexes formed by the Li⁺ cation with all the isotopomers of the hydrogen molecule is solved by the variational method using sufficiently exact nonempirical adiabatic surfaces of the potential energy and the dipole moment. Information on the largeamplitude vibrations was obtained for the first time, and the anharmonic effects caused by the interaction of the different internal degrees of freedom in these weakly bound van der Waals complexes were consistently taken into account. The frequencies and intensities of many spectral transitions are determined, and the average values of geometrical parameters and the dipole moment are calculated for the ground and excited vibrational states.     

An IR spectroscopic study of liquid ozone and ozone dissolved in liquid argon

We have measured and interpreted the IR spectra of liquid ozone films at 78–85 K and ozone dissolved in liquid argon at 91–95 K. A less hindered rotation of ozone molecules in argon manifests itself as an intensity redistribution, caused by the Coriolis interaction, from the states ν₃(B ₁) and ν₁ + ν₃(B ₁) to the states ν₁(A ₁) and 2ν₁(A ₁), respectively. The occurrence of wings in the contours of the bands ν₁(A ₁), 2ν₁(A ₁), and 2ν₃(A ₁) in liquid Ar and their absence in the spectrum of O₃ also confirms the conclusion that the rotational motion of ozone molecules in an inert solvent at low temperatures is relatively less hindered. Maxima of ozone bands in Ar solution are shifted toward lower frequencies compared to those in the gas phase by 1–30 cm^?1, which corresponds to the following shifts of harmonic frequencies of the molecule: Δω₁ = ?1.85(5) cm^?1, Δω₂ = ?0.67(7) cm^?1, Δω₃=?7.20(5) cm^?1. It was found that the absorption band of the ν₃ mode in the spectrum of O₃ in the liquid phase has a complicated asymmetric contour because of the resonance dipole-dipole interaction. The first and second spectral moments of this band have been determined to be M ₁ = 1030.6 cm^?1 and M ² = 240.0 cm^?2.