High-pressure FT IR measurements of crystalline methylene chloride up to 120 kbar in the diamond anvil cell

The FT IR spectra of pressure-induced crystalline CH₂Cl₂ at room temperature were measured at hydrostatic pressures up to 120 kbar in the diamond anvil cell. The pressure dependences of the internal modes (ν₃, ν₉, ν₈, and ν₂) are reported and compared with the result of Raman scattering measurements. The discontinuity of the slope (dν/dP) at ≈ 45 kbar for the ν₉ antisymmetric CCl streching mode indicates the pressure-induced second-order phase transition which seems to be triggered by the interaction between the ν₉ mode and the ν₃ symmetric CCl stretching mode.     

Spectroscopy at very high pressures: Infrared study of the high pressure phase transitions in NaNO2 and KNO2

Infrared spectra of NaNO₂ and KNO₂ in the region of the anion internal modes have been obtained using a diamond anvil cell at pressures up to 65 kbar. At 39°C NaNO₂ undergoes a phase transition at ca. 10.0 kbar, not at 14 kbar as reported from an earlier IR study. A similar transition was found at 6.3 kbar for KNO₂. The symmetric modes lose intensity with increasing pressure, and all modes suffer blue-shifts. For KNO₂ ν(NO)₅ shifts much more than ν(NO)_a.     

Continuous and discontinuous phase transitions in ammonium halides

Raman spectra of NH₄Cl and NH₄Br have been recorded as functions of temperature and pressure. The λ-type phase transition in NH₄Cl has been studied as (i) a weakly first order. (ii) a tricritical and (iii) a second order transition. A strongly first order transition has been studied in NH₄Br. The analysis of the data has concentrated on the correlation of frequency shift with volume change across the phase change regions. This correlation has been established for the frequencies of the ν₂ and ν₅ Raman modes of NH₄Cl at zero pressure (1st order) 1.6 kbar (tricritical) and 2.8 kbar (2nd order), and the frequencies of the ν₅ Raman mode of NH₄Br at zero pressure (1st order). A single Y (mode Grünelsen parameter) has been shown to describe each frequency shift right through the phase change region once an order-disorder contribution has been introduced at and below the transition temperatures.     

Phase behavior of Li2WO4 at high pressures and temperatures

The phase diagram of Li₂WO₄, previously studied by Yamaoka et al. (J. Solid State Chem.6, 280 (1973)) has been revised. Li₂WO₄ II is stable at atmospheric pressure below ～310°C. This phase appears to be a modified spinel, and is tetragonal, a, c = 11.941, 8.409Å, Z = 16, space group $\text{I4}{}_1\text{amd}$. The melting curve of phenacite-type Li₂WO₄ I rises with pressure with a slope of 0.9°C/kbar to the III/I/liquid triple point at 3.1 kbar, 743°C, beyond which the melting curve of orthorhombic Li₂WO₄ III rises steeply with pressure (initial slope 31°C/kbar). The Li₂WO₄$\text{I}\text{III}$ transition line at 3 kbar is almost independent of temperature, i.e., the $\text{I}\text{III}$ transition entropy is zero. Li₂WO₄ II is 21.3% denser than Li₂WO₄ I at ambient conditions.     

Solid-state vibrational spectroscopy: Part VI. An infrared and raman spectroscopic study of transition metal(II)4-methylpyridine complexes

Infrared (4000–200 cm^?1) and Raman (3500–300 cm^?1 ) spectra are reported for metal(II) halide and thiocyanate 4-methylpyridine complexes of the following stoichiometries: (MX₂(4-Mepy)₂) {M = Mn, Co, Cu or Zn, X = Cl or Br; M = Mn, Ni or Zn, X = NCS}; (MX₂(4-Mepy)₄) {M = Mn, Fe, Co or Ni, X = Cl or Br; M = Mn, Fe, Co, W or Cu, X = NCS}. For a given series of isomorphous complexes there is a correlation between the sum of the differences between the liquid and ligand values of the ν₁, ν₂, ν₃, ν₄, ν₅, ν₆, ν₇, ν₈, ν₉, ν₁₀, ν₁₂, ν₁₃ and ν₁₄ modes of 4-methylpyridine and the strength of the metal-nitrogen bond. Comparison of the shift values of pyridine and 4-methylpyridine complexes supports the suggestion that, unlike the situation in the pyridine complexes, back-donation from the metal to the ligand is unimportant in the 4-methylpyridine complexes.     

Melting curve and high-pressure polymorphism of NH4HF2

The melting curve of NH₄HF₂ I rises from 125.2°C at atmospheric pressure to a triple point II/I/liquid at 9.3 kbar, 220°C. The I/II phase boundary is terminated at a triple point III/I/II at ∼45 kbar, 295°C. The melting curve of the new phase NH₄HF₂ II passes through a broad maximum at ∼39 kbar, 306°C, and is terminated at a triple point III/II/liquid at 46.3 kbar, 301°C. The melting curve of NH₄HF₂ III rises with pressure. The NH₄HF₂ III may be a dense hydrogen-bonded phase. Liquid NH₄HF₂ appears to be anomalous in several respects, and has a high compressibility relative to the solid phases.     

Sub-solidus Relations in the System KF—PbF2 to high Pressures

The phase β-K_0.25Pb_0.75F_1.75 previously found in the KF-PbF₂ system appears to be metastable at low temperatures relative to a mixture of orthorhombic PbF₂ and a new phase suspected to be KPbF₃ II. KPbF₃ II transforms to KPbF₃ I at 298.5°C at atmospheric pressure. The KPbF₃ II/I transition line rises with pressure, but the substance appears to reversibly disproportionate above ～360°C, 5 kbar, possibly to a mixture of PbF₂ and K₄PbF₆. Instead of β-K_0.25Pb_0.75F_1.75, a mixture with this composition yielded, in addition to weak heat events due to the KPbF₃ II/I transition, strong heat events at 254.5°C and atmospheric pressure (thermal hysteresis ～13°C) which were ascribed to the PbF₂ orthorhombic/cubic transition. This transition rises with pressure to 673°C at 37.8 kbar.     

FT-Raman and high-pressure infrared spectroscopic studies of dicalcium phosphate dihydrate (CaHPO4·2H2O) and anhydrous dicalcium phosphate (CaHPO4)

The FT-Raman spectra and the pressure dependence of the infrared spectra of the hydrated and anhydrous forms of dicalcium phosphate, CaHPO₄ · 2H₂O and CaHPO₄, have been studied. The hydrated salt exhibits a phase transition at 21 kbar (1.0 kbar=0.1 Gpa) but no high pressure transition was observed for anhydrous dicalcium phosphate. The O–H stretching frequencies of the water molecules in CaHPO₄·2H₂O all showed negative pressure dependences and correlate with the OO distances. The PO–H stretch increased with increasing pressure, indicating a strong hydrogen bond. The frequencies associated with the phosphate ion showed a normal pressure dependence.     

Vibrational relaxation of liquid dichloromethane at high pressure

The Raman spectra of two symmetric bands ν₁ and ν₃ of CH₂Cl₂ have been measured as a function of pressure to 300 MPa (3 kbar) and over the temperature range 303–363 K. For all bands the isotropic width increases with inreasing pressure and temperature. The experimental vibrational relaxation times are compared with the predictions of different combination of mass factors using the Fischer—Laubereau vibrational dephasing model.     

FTIR spectra of the 2ν4, ν4 + ν6 and 2ν6 bands of formaldehyde

High resolution IR spectra of the overtones and the combination band of the ν₄ and ν₆ modes of formaldehyde (2ν₄, ν₄ + ν₆ and 2ν₆) were measured in the region of 2200–2650 cm⁻¹ using FTIR. The combination band ν₄ + ν₆, whose dipole transition is forbidden from molecular symmetry, was observed due to the intensity borrowed from the other bands. The observed frequencies were analysed by a Hamiltonian in which A-type Coriolis interactions and Darling—Dennison interaction were taken into account. The ratio and the relative signs of the transition dipole moments of the overtone bands, μ_2ν4 and μ_2ν6, have been determined by analysing the intensity distribution of the vibration—rotation lines.     

Photoacoustic study of CH4(ν3) deactivation by collisions with rare gases

CH₄(ν₃) deactivation is studied in the gas phase by the photoacoustic method at 300 K. Rapid vibration-to-vibration transfer holds the adjacent levels in a quasi-equilibrium distribution. The vibrational levels can then be grouped in two sets: (ν₂, ν₄) on the one hand and (ν₃, ν₁, 2ν₂, 2ν₄, ν₂ + ν₄) on the other. By successive dilution of CH₄ in He, Ne, Ar, we determined the vibration-to-translation-rotation rate constants characterizing the deactivation of each set. The vibration-to-vibration intermolecular rate constant which connects the two sets is also obtained.     

Phase transitions in the dimethyl thallium(III) halides, (CH3)2TIX(X = Cl,Br, I)

The dimethyl thallium(III) halides were investigated at low temperature and at high pressure by IR and Raman spectroscopy. These compounds have a tetragonal structure under ambient conditions, in which the methyl groups are disordered. Ordering transitions were observed at low temperature in all three halides. The low-temperature unit cells are monoclinic or triclinic with C_2h or C_i symmetry and Z = 1 and Z = 2 per primitive unit cell for the chloride and for the bromide and iodide, respectively.At high pressure, the iodide and bromide underwent phase transitions at just below 10 kbar to phases similar to those observed at low-temperature. A second transition was observed in both the iodide and bromide at 27 and 45 kbar, respectively, which involved a change in conformation of the (CH₃)₂Tl⁺ ion from linear to bent and a distortion of the (TlX)_nlayers. Significant spectral changes were also observed for the iodide and bromide at close to 65 kbar and 70 kbar, respectively, indicating the presence of another transition involving a change in methyl group orientation.The chloride underwent a transition at about 15 kbar at which the methyl groups become ordered. This phase appears to be related to that observed at low-temperature for the bromide and iodide. Further changes were observed at just below 25 kbar indicating that the (CH₃)₂Tl⁺ ions become bent. There is evidence for another transition above 35 kbar from changes in slope on plots of ν versus p.     

Lithium isotope effects in the vibrational spectra of Li2SeO4

Polarized Raman scattering spectra have been measured in single crystal ⁷Li₂SeO₄ and ⁶Li₂SeO₄. Based on these data, symmetry-based band assignments are proposed for the ν₂, ν₄ and lithium mode regions. Vibrational coupling interactions are noted between the ν₂, ν₄ and the lithium translatory modes.     

Vibrational spectroscopy at high pressure: Part 53. Alkali metavanadates and copper metagermanate

Essentially complete Raman and infrared spectra at ambient and 80 K have been obtained for the isostructural metavanadates AVO₃, (A  K, Rb, Cs). An assignment is offered on the basis of line and factor group analyses. A similar study has been made on CuGeO₃. Under pressure up to 100 kbar both KVO₃ and RbVO₃ show a single phase transition, at 56 and 53 kbar. The remarkable insensitivity of the transition pressure to change of cation implies that the major effect of pressure is chain torsion and repacking, driven by the need to reduce the cation coordination number.     

Pressure-tuning Raman and infrared spectra of N-thiocyanato[tris(o-tolyl)]tin(IV), (o-CH3C6H4)3SnNCS

The effect of high external pressures on the Raman and IR spectra of the title compound (I) has been examined at ambient temperature. A pressure-induced phase transition was observed at 13–16 kbar, which is most likely second-order, resulting from slight rotations of the phenyl rings and/or the CH₃ groups under the influence of pressure. No new peaks were observed in the spectra with increasing pressure indicating that no pressure-induced linkage isomerism or SnNCS⋯Sn bridging took place. The average pressure sensitivity (dν/dP) of the Raman-active vibrational modes is lower in the low-pressure region (0.23 cm⁻¹/kbar) than in the high-pressure one (0.47 cm⁻¹/kbar). In general, the IR-active modes are less sensitive to increasing pressure than are the Raman-active modes and the average dν/dP value for the IR-active modes in the low-pressure region is quite similar to that in the high-pressure region, i.e., about 0.23 cm⁻¹/kbar.     

Vibrational relaxation in the group IVA trimethylmetal chlorides

The temperature dependence of the polarized and depolarized Raman spectra of the ν₂, ν₄, ν₆ and ν₇ modes were measured for t-butyl chloride and the analogous group IVA trimethylmetal chrlorides (silicon, germanium and tin). Analysis of the lineshapes revealed that isotropic second moments and vibrational relaxation times for a given mode remained approximately constant through the series. This tranferability of relaxation parameters between molecules extended to modulation times calculated from the Kubo formalism. The above results are in contrast to earlier studies on molecules of dissimilar structure. They provide some preliminary evidence that the mechanism of vibrational relaxation may be the same for equivalent modes in members of the series.     

Vibrational spectroscopy at high pressures—57 [1]. Phosphonitrilic chloride trimer and tetramer

Raman and IR spectra at high pressures are reported for (PNCl₂)₃ and (PNCl₂)₄. The trimer exhibits a second order phase transition near 22 kbar to a structure of probable monoclinic symmetry, whilst the tetramer shows evidence of a similar change near 10 kbar.     

Infrared spectra of B(OMe)3, ClB(OMe)2 and Cl2BOMe species,isolated CH stretching frequencies and bond strengths

Infrared spectra in the gas phase are reported over the range 3100-500 cm⁻¹ for species of B(OMe)₃, ClB(OMe)₂ and Cl₂BOMe, with CH₃, CD₃ and CHD₂ substitution. A detailed analysis of νCH and νCD data in all three species of Cl₂BOMe yields strong evidence for the presence of three kinds of CH bond, two of them weak and one of them strong. The methyl group is then twisted, probably through 10–20°, out of the eclipsed or staggered conformation. The CHD₂ spectra of the di and trimethoxy compounds are less susceptible to analysis, but suggest also the presence of two weak and strong bonds, the former increasing in weakness as the number of methoxy groups increases. This is as expected from the increased competition likely between the lone pair electrons for the empty boron orbital. The spectra of the CD₃ species permit a clear assignment of νBO, δ_sCH₃, δ_sCD₃ and δ_asCD₃ modes. In Cl(COCH₃)₂, ν_sBO lies at 1278 cm⁻¹.     

Vibrational-translational/rotational and vibrational-vibrational processes in methane: Optoacoustic measurements

Both V-T,R and V-V processes in methane have been studied optoacoustically following excitation of the ν₃ level with a He-Ne laser at 2947.9 cm^?1. The lifetime of the V-T,R process is 1.55 ± 0.05 μs atm. The rate constants for the fast equilibration between the bending modes is k(ν₂ → ν₄) = 60 μs^?1 atm^?1 and k(ν₄ → ν₂) = 13 μs^?1 atm^?1. The decay of the ν₃ and ν₂ stretching modes, which are in very rapid equilibrium, shows a rate constant of 0.23 ns^?1 atm^?1 and, within experimental error, produces exclusively the ν₄ stretching mode. Part of this decay, 4.6%, is by a single-quantum process producing a large amount of translational/rotational energy; the dominant process, 95.4%, is double-quantum through the 2ν₄ overtone. Both the yield of the single-quantum process and the exclusive production of the ν₄ bending mode from the (ν₃, ν₂) level are in dispute with current theoretical models.