Vibrational spectra of the ammonia halides NH4I and NH4F at high pressures

The vibrational spectra of ammonium iodide NH₄I at pressures up to 4.1 GPa and ammonium fluoride NH₄F at pressures up to 4.7 GPa were investigated by inelastic incoherent neutron scattering. The pressure dependences of the transverse optical translational and librational modes were obtained. The behavior of the rotational potential barrier for the ammonium ion as a function of the lattice parameter for disordered and ordered cubic phases of ammonium halides with CsCl type structure were calculated. The results obtained confirm that the transition from an orientationally disordered cubic phase into an ordered cubic phase in ammonium halides occurs at close critical values of the positional parameter of hydrogen (deuterium).     

Raman study of NH4CI at high pressures

Abstract

The Raman spectrum of ammonium chloride has been carefully studied in the vicinity of its Λ-transition. Spectra were recorded as a function of temperature under various fixed pressures close to 1.6 kbar, which is the pressure required to make the Λ-transition become second order. The critical exponents derivable from the spectroscopic data seem to be as reliable as those from other types of data, even in the multicritical region.     

Ultraviolet thermoreflectance spectra of NH4Br in phases II and III

Thermoreflectance spectra of NH₄Br in the energy range from 5.5 to 9.5 eV have been measured between room temperature and liquid-nitrogen temperature. The influence of the ordering of the ammonium tetrahedra has been studied. Near the transition point the thermoreflectance Δ at the first exciton peak shows a behaviour similar to that of the specific heat. Furthermore, the temperature dependence of the spin-orbit splitting of the Γ-exciton is considered.     

Structural study of ND4Br at high pressure

Abstract

A structure of ND₄Br has been studied at pressures up to 9 GPa by means of time-of-flight neutron diffraction. A phase transition to the high pressure phase V was observed at P=8·2(5)GPa. It was found that the phase V has a tetragonal structure with an antiparallel ordering of ammonium ions, space group P4/nmm which is in strong resemblance with low temperature modification ND₄Br(III). Deuterium positional parameter as a function of pressure was obtained.     

Ammonium ion dynamics in NH4Br at high pressure - type of reorientation

Abstract

Proton NMR relaxation measurements were performed for ammonium bromide at pressures up to 800 MPa. The correlation functions for ammonium ion reorientation were calculated by Monte Carlo method. Knowledge of these functions allow calculation of the NMR relaxation times T₁. Comparison between experimental and calculated values of relaxation times gives some insight into the model of ammonium ion reorientation.     

X-ray diffraction and Raman spectra of merrillite at high pressures

ABSTRACT

The compressibility and effect of pressure on the vibrations of merrillite, Ca₉NaMg(PO₄)₇, were studied by using diamond anvil cell at room temperature combined with in-situ synchrotron X-ray diffraction and Raman spectroscopy up to about 18 and 15?GPa, respectively. The pressure-volume data was fitted by a third-order Birch–Murnaghan equation of state to determine the isothermal bulk modulus as K₀ ?=?87.2(32) GPa with pressure derivative K₀′?=?3.2(4). If K₀′?=?4, the isothermal bulk modulus was obtained as 81.6(10) GPa. The axial compressibility was estimated and an axial elastic anisotropy exists since a-axis is less compressible than the c-axis. The Raman frequencies of all observed modes for merrillite continuously increase with pressure, and the pressure dependences of stretching modes (v ₃ and v ₁) are larger than those of the bending modes (v ₄ and v ₂) and external modes. The isothermal mode Grüneisen parameters and intrinsic anharmonicity of merrillite were also calculated.     

Vibrational spectroscopy at high pressures. Part 50. A Raman scattering study of MSCN (M = K,Rb, Cs,NH4) at high pressures

The phase behaviour of the title compounds was studied at high pressures using Raman spectroscopy. The isostructural materials KSCN and RbSCN show two phase changes (12.5 and 45.5 kbar; 10.5 and 37.5 kbar, respectively) which appear to be second order in type. Structures and transition mechanisms are proposed for each phase. CsSCN has a different orthorhombic structure and shows only one phase change in the range studied, at 23.5 ± 1.5 kbar, which also seems to be second order. The known phase transition in NH₄SCN at 2 kbar has been confirmed, and a new one found at 10 kbar. A monoclinic cell is proposed for the new phase.     

Thermodynamic parameters of solids at high pressures from vibrational spectroscopy: MgO and MgAl2O4

Abstract

The effect of pressure on the optical or acoustic modes in the sideband fluorescence of Cr³⁺ doped into the MgO and MgAl₂O₄ lattices was identical to that measured for the corresponding Raman and infrared modes of MgAl₂O₄ and ultrasonic sound velocities (Chang and Barsch 1973, Jackson and Niesler 1982) for both MgO and MgAl₂O₄. This shows that the impurity cation does not measurably perturb the crystal lattice vibrations and thus may be used to probe the thermodynamic properties of such cubic materials at high pressures. The effect of pressure on the heat capacity, C_V, and entropy, S, of MgO and MgAl₂O₄ spinel was determined using statistical thermodynamics on the lattice vibrations measured to over 200 kbar. The results for MgO are identical to predictions from Debye theory to at least 10% compression.     

Structural study of ND4I at high pressures and low temperatures

Abstract

Structure, positional, and thermal parameters of ND₄I were studied at high pressures up to 90 kbar and low temperatures down to 10 K using time-of-flight neutron diffraction. The phase transition from a disordered CsCI-type cubic phase ND₄I(II) into a recently discovered high pressure phase ND₄I(V) was observed at P = 80(5) kbar. Surprisingly, the structure of the high pressure phase V was found to bear a strong resemblance to that of the ambient pressure, low-temperature phase III - tetragonal structure with an antiparallel ordering of ammonium ions, space group P4/nmm. The critical value of the deuterium positional parameter corresponding to the II-V transition is close to the one for the phase transition between the disordered and ordered CsCl-type cubic phases II and IV in other ammonium halides.     

Experimental and theoretical studies of the vibrational spectra of CHD2Br

The dideuterated form of methyl bromide, CHD₂Br, has been synthesized and the gas-phase infrared spectra investigated in the range 400–10,000?cm^–1 using a medium-resolution FTIR spectrometer. The nine fundamental bands have been characterized in detail. Six of them, i.e. ν ₁, ν ₄, ν ₅, ν ₇, ν ₈ and ν ₉, have been rotationally analysed through the assignment of the partially resolved structure of the ^PQ_K and ^RQ_K cluster of lines and the spectroscopic parameters have been derived in the symmetric top limit approximation. Among the fundamental levels, anharmonic resonance occurs between ν ₇/ν ₄?+?ν ₈ and ν ₈/ν ₆?+?ν ₉. An isotopic ^79/81Br shift was found for ν ₆ and in the more complex region of the ν ₈ fundamental. High-quality ab initio calculations – carried out at coupled cluster level [CCSD(T)] employing the correlation-consistent basis set of Dunning (cc-pVTZ) – were performed to determine quadratic, cubic and quartic (semidiagonal) force constants. Using these constants and applying second-order vibrational perturbation theory (VPT2), with allowance for resonances (when necessary), permitted us to identify and assign, in addition to the fundamentals, about 70 overtones and combination bands up to three quanta.     

Raman spectra of forsterite and fayalite at high pressures and room temperature

Abstract

Raman spectra of the two pure end-members of olivine (forsterite and fayalite) were studied at high pressures and room temperature in a diamond-anvil cell using both single-crystals and polycrystalline samples in pressure mediums of either an ethanol-methanol mixture or H₂O. Variations with pressure were studied up to 170kbar for fayalite and to 300kbar for forsterite. Two intensive Raman bands of fayalite were definitely observable at high pressures, but only one of them can be reliably determined. Both have a linear variation within experimental uncertainty. Because of interference from the high spectral background, we found that nearly all the weak bands of forsterite could not be reliably determined at high pressures. However, the pressure variations of all bands of forsterite which can be reliably determined are non-linear. The rates of frequency change for the intense bands of forsterite determined in the present experiment are consistent with those of natural forsterites determined by Besson et al. ¹ and Gillet et al. ², but are in a slight discordance with those reported by Chopelas³. Furthermore, there is no evidence for the olivine ? spinel phase transition occurring at room temperature.     

The Mössbauer effect of SnI4 at high pressures

Tetravalent tin iodide is a molecular crystal composed of SnI₄ tetrahedra loosely packed into a cubic configuration. Under pressure SnI₄ becomes metallic at about 15 GPa. We report a Mossbauer effect study of¹¹⁹Sn and¹²⁹I in SnI₄ to pressures of 26 GPa. The spectra exhibit dramatic changes with pressure starting at about 10 GPa and show large pressure hysteresis effects upon reducing the pressure from 26 GPa. In the intermediate region tin exists in both Sn⁴⁺ and Sn²⁺ states, and iodine exists in two nonequivalent sites characterized by a different symmetry and different sign and magnitude of the electric field gradient.Supported by US DOE, BES-Materials ScienceVisiting Scientist, Tel-Aviv University, 69978 Ramat Aviv, IsraelNow at Teledyne Brown Engineering, Huntsville AL 35807 USA     

用代数哈米顿量研究CH3C1分子的振动谱

我们提出一种描述XH3分子的伸缩和弯曲振动的U(2)代数哈米顿量,其中包括了伸缩和弯曲振动的费米共振耦合;用它来拟合CH3Cl分子的实验数据,结果表明有较少参数的代数模型算得的偏差比其它模型算得的偏差要小.     

用代数哈米顿量研究CH_3Cl分子的振动谱(英文)

我们提出一种描述XH3分子的伸缩和弯曲振动的U(2)代数哈米顿量,其中包括了伸缩和弯曲振动的费米共振耦合,用它来拟合CH3Cl分子的实验数据,结果表明有较少参数的代数模型算得的偏差比其它模型算得的偏差要小.     

Absorption spectra of NH4MnCl3 and NH4MnF3

The absorption spectra of NH₄MnCl₃ and NH₄MnF₃ crystals have been measured down to 10 K in the 250 to 600 nm region. The observed bands are assigned to electronic transitions from the ⁶A_1g(S) ground state to various excited levels of Mn²⁺ ions in an octahedral crystalline field. The position of the bands have been fitted within the strong crystal field scheme. Resulting parameters at room temperature are B=741, C=2990 and Dq=520 cm⁻¹ for NH₄MnCl₃ and B=800, C=3139 and Dq=694 cm⁻¹ for NH₄MnF₃. At low temperature some bands show a rich fine structure in which some phonon progressions have been identified.     

The Raman spectra of NH4I at high pressures. The existence of a new phase in the ammonium halides

The Raman spectra of NH₄I and ND₄I show significant changes at higher pressures which can only be interpreted in terms of the existence of a new phase. This is not an intermediate phase occurring between phases II and IV, but is observed upon further compression of the ferro-ordered phase IV. Preliminary measurements show that the same phase transition occurs in NH₄Br and NH₄Cl, but at significantly higher pressures than the one in NH₄I.     

Ultraviolet reflectivity of NH4Cl and NH4I in ordered and disordered phases

Near-normal incidence reflectivity spectra below 10 eV of NH₄Cl in phases II and IV and of NH₄I in phases II and III are reported. An interpretation is given by comparing these spectra with those of alkali halides. A temperature shift of the first exciton peak of NH₄I due to ordering of the crystal was found as was the case with NH₄Br. The absence of this effect in NH₄Cl strongly implies the relation to the transition II–III and the tetragonal distortion of the lattice.     

The ν4 state inversion spectra of 15NH3 and 14NH3

The frequencies and assignments of 45 inversion transitions of ¹⁵NH₃ and 15 additional inversion transitions of ¹⁴NH₃ in the ν₄ state are reported. The J = 0 inversion frequency and K-type doubling constant for K,l = 2, ?1 are 31 602.72 MHz and 2.000 MHz for ¹⁵NH₃. The expression containing the effective l-type doubling constant, q₀ - 5q_J - Δη…, is calculated from the (J,K,l) = (1,1,1), (1,1,?1), (2,1,1), and (2,1,?1) transitions as 10 166.022 MHz. The contribution to this expression from the Coriolis coupling with 2ν₂ is estimated for ¹⁴NH₃.