T. D. Kolomiitsova

Absorption spectrum of the (CF4) dimer in liquid argon solution

The concentration dependence of the shape of absorption bands in the spectrum of CF4 in liquid argon is studied in the concentration range (0.01–17)×10−3 molar fractions at 93 K. In all spectral regions related to ν3, the shape of the spectral function is determined, along with the Fermi resonance 〈νi,ν3+1,ν4|≈〈νi,ν3,ν 4+2|, by the resonance dipole-dipole interaction. In the spectral region of the Fermi doublet ν 1+ν3≈ ν1+2ν4, the spectrum of the contact (CF4)2 dimer is identified. Agreement between this spectrum and the calculated spectrum is achieved by simultaneously taking intramolecular and intermolecular resonances into account. The distance RC-C in the dimer is 4.85(15) Å. The calculations of the spectra of (12CF4)2 and (13CF4−12CF4) dimers with this value of RC-C in the region ν 3≈2ν4 agree with the experiment.

Integral Intensities of Absorption Bands of Silicon Tetrafluoride in the Gas Phase and Cryogenic Solutions: Experiment and Calculation

The spectral characteristics of the SiF4 molecule in the range 3100–700 cm−1, including the absorption range of the band ν3, are studied in the gas phase at P = 0.4–7 bar and in solutions in liquefied Ar and Kr. In the cryogenic solutions, the relative intensities of the vibrational bands, including the bands of the isotopically substituted molecules, are determined. The absorption coefficients of the combination bands 2ν3, ν3 + ν1, ν3 + ν4, and 3ν4 are measured in the solution in Kr. In the gas phase of the one-component system at an elevated pressure of SiF4, the integrated absorption coefficient of the absorption band ν3 of the 28SiF4 molecule was measured to be A(ν3) = 700 ± 30 km/mol. Within the limits of experimental error, this absorption coefficient is consistent with estimates obtained from independent measurements and virtually coincides with the coefficient A(ν3) = 691 km/mol calculated in this study by the quantum-chemical method MP2(full) with the basis set cc-pVQZ.

Effects of pair resonant dipole-dipole interactions on the formation of band profiles in infrared absorption spectra

Resonant dipole-dipole interactions are shown to play a crucial role in forming the profiles of several bands in the fundamental and overtone regions of the vibrational spectrum for molecules with a relatively large first derivative of the dipole moment (P′>0.3 D). Analytic expressions are derived for the probability density of the matrix element for the interaction of one-and two-dimensional oscillators. We computed the band profiles in the infrared absorption spectrum for a pair of molecules at a fixed distance R ∼ 5 Å, typical of condensed media. Comparison is made with experimental data for low-temperature condensed systems: matrices and solutions in liquefied gases.

Vibrational spectra of monoisotopic SiH4 and GeH4 in low-temperature matrices

IR absorption spectra of monoisotopic 28SiH4 and 76GeH4 are studied in Ar and N2 matrices at 10 K. It is shown that the absorption spectra of silane and germane are similar in the regions of the stretching ν3 and bending ν4 vibrations. Four groups of bands can be separated out in the spectra of each molecule: (1) narrow bands characteristic of the matrix isolation studies, (2) broad bands, (3) diffuse absorption with a large value of the spectral moment M2* the intensity of which increases upon annealing, and (4) bands of dimers the intensity of which increases quadratically with concentration. The spectra of 28SiH4 and 76GeH4 in nitrogen matrices contain a triplet in the stretching region and a doublet in the bending region, which is explained by the change in the molecular symmetry from Td to C3V on passage from the gas phase to solid nitrogen.

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(B1) and ν1 + ν3(B1) to the states ν1(A1) and 2ν1(A1), respectively. The occurrence of wings in the contours of the bands ν1(A1), 2ν1(A1), and 2ν3(A1) 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 M1 = 1030.6 cm−1 and M2 = 240.0 cm−2.

Structures of vibrational absorption bands of the SiF4 molecule in a low-temperature nitrogen matrix

We have studied the IR absorption spectra of diluted mixtures SiF4/M = 1/6000–1/10 000 in an N2 matrix at 11 K (for comparison, the spectra of SiF4 in Ar and Xe matrices have also been studied). It has been shown that, in solid nitrogen, the appearance of doublets is observed both in the range of the ν3 band of the SiF4 (28SiF, 29SiF4, and 30SiF4) isotopologues of the SiF4 molecule and in the range of the ν1 + ν4, ν2 + ν3, and ν1 + ν3 bands of 28SiF4, whereas, in the range of the 2ν3 band of 28SiF, a triplet appears. In order to analyze the influence of the matrix on the spectrum of free SiF4 molecules, we have used a model that makes it possible to successively calculate (i) the spectrum of SiF4 in terms of the model of local modes, (ii) the structure of a matrix composed by 864 N2 molecules + a rigid SiF4 molecule using the Monte Carlo method, and (iii) the interaction of matrix particles with local dipole moments in the approximation of dipole-induced dipole and dipole-quadrupole interactions. The model describes satisfactorily the low-frequency shift of bands in the nitrogen matrix. All obtained experimental and theoretical results are consistent with the assumption that two kinds of stable trapping centers of SiF4 molecules obeying the Td symmetry are realized in the nitrogen matrix.

Study of cluster formation in low-temperature systems. Spectral manifestation of resonance dipole–dipole interactions between nondipole polyatomic molecules

Resonance dipole-dipole interactions are shown to strongly manifest themselves in fundamental and overtone band shapes of low-temperature systems consisting of polar and nonpolar molecules as well with a relatively large first derivatives (P′>0.3D) of the dipole moment. A rough model on the basis of the interaction between two non-degenerate, doubly degenerate, and triply degenerate oscillators was developed to study pairs of interacting molecules and clusters in low-temperature condensed systems. The concentration dependences of second- and third-order spectral band moments made it possible to estimate the number of molecules in clusters.

Spectroscopic parameters of CHFCl2, CHClF2, C2F6, and C3F8 molecules

We investigate the IR spectra of solutions of R-21,-22,-116, and R-218 in liquid argon at 90K. The frequencies, half-widths, and absolute integral intensities of all of the absorption bands recorded are obtained and interpreted.

Isotope shifts in spectra of molecular liquids

In the IR absorption spectra of low-temperature molecular liquids, we have observed anomalously large isotope shifts of frequencies of vibrational bands that are strong in the dipole absorption. The same effect has also been observed in their Raman spectra. At the same time, in the spectra of cryosolutions, the isotope shifts of the same bands coincide with a high accuracy (±(0.1–0.5) cm–1) with the shifts that are observed in the spectra of the gas phase. The difference between the spectra of examined low-temperature systems is caused by the occurrence of resonant dipole–dipole interactions between spectrally active identical molecules. The calculation of the band contour in the spectrum of liquid freon that we have performed in this work taking into account the resonant interaction between states of simultaneous transitions in isotopically substituted molecules can explain this effect.

Observation of simultaneous ν1(SF6) + ν3(NF3) and ν2(SF6) + ν3(NF3) transitions enhanced by the resonance dipole-dipole interaction with the ν1 + ν3 and ν2 + ν3 states of the SF6 molecule

IR spectra of the solution of SF6 molecules in liquid NF3 at 84 K have been recorded. In a solvent transmission window of 1500–1750 cm−1, two wide absorption bands with pronounced peaks in the high-frequency part are observed. The profile of these bands is explained by the influence of the resonance dipole-dipole (RDD) interaction of the states of the simultaneous transition ν1(SF6) + ν3(NF3) and ν2(SF6) + ν3(NF3) with the states (ν1 + ν3) and (ν2 + ν3) of the SF6 molecules, respectively. The use of three isotopic modifications 32SF6, 33SF6, and 34SF6 has allowed us to vary the resonance detuning and thus to change the strength of the RDD interaction. With the liquid near the melting point being represented as a close-packed cubic crystal, the profile was calculated and its spectral characteristics were determined. The frequencies of the main peaks coincide with the experimental values accurate to the error.