Raman study of charge-density-wave phase transition in quasi-one-dimensional conductor (TaSe4)2I

Polarized Raman spectra were obtained in the quasi-one-dimensional conductor (TaSe₄)₂I above and below the charge-density-wave (CDW) transition temperature (T_c=263 K). The Raman intensities of many peaks become intenser and two of the phonon peaks shift to higher frequency with decreasing temperature. Moreover a new broad peak at about 90 cm^?1 and a new peak around 166 cm^?1 appear in the low-temperature phase. The polarization characteristic shows that the former is assigned to totally symmetric mode. The damping constant of the phonon at 90 cm^?1 increases markedly with increasing temperature. The frequency shifts to higher frequency as the temperature increases and the coupling coefficient is approximately proportional to (T_c?T)^{$\text{1}\text{2}$}. This peak becomes Raman active owing to the CDW phase transition. The temperature dependence of the damping constant and the frequency shift may have a relation to the dynamical properties of the CDW phase transition.     

The vibrational spectra of magnesium pyrophosphate polymorphs

The Raman spectra were measured and analyzed for both α- and β-Mg₂P₂O₇. The IR and Raman spectra were interpreted for both phases using factor group analyses. The spectral features predicted with factor groups arising from the X-ray crystallographic space groups $\text{P2}{}_1\text{c}$ ? c⁵_2h and $\text{C2}\text{m}$ ? C³_2h for α-Mg₂P₂O₇ and β-Mg₂P₂O₇, respectively, fit the observed results. Bands observed in the Raman spectrum for β-Mg₂P₂O₇ are consistent with a linear bond angle while those for α-Mg₂P₂O₇ are consistent with a bent P-O-P bond angle. No soft modes were observed in the Raman spectra indicating that the phase transition between the two phases is not a second order process.     

Raman spectroscopic study of tris-sarcosine calcium chloride in the antiferroelectric phase

The polarized Raman spectra of (CH₃NHCH₂COOH)₃CaCl₂ (TSCC) have been obtained applying hydrostatic pressure in the paraelectric, ferroelectric and in the pressure-induced antiferroelectric phase. The phase transition between the paraelectric or the ferroelectric and the antiferroelectric phase appears to be of first order. No cell doubling could be observed in the antiferroelectric phase. The space group $\text{P2}{}_1\text{a (C}{}^5{}_{\mathrm{2h}}\text{)}$ for TSCC in this phase is compatible with our experimental results. The pressure-dependence of the Raman-active soft mode is discussed qualitatively.     

Infrared study of superlattice formation in Ti1+xSe2

Infrared reflectivity measurements have been made on two Ti_1+xSe₂ crystals of different stoichiometry over the range 200 cm^?1 to 4000 cm^?1 before and after the formation of a 2a_o × 2c_o superlattice. In both crystals at room temperature a heavily damped Drude edge is observed at about 1000 cm^?1. At liquid helium temperatures, below the phase transition, the Drude minimum of a non-stoichiometric crystal ($\text{x ? 0.02, T}{}_{\mathrm{c}}\text{= 155 K}$) is at 750 cm^?1 whereas the low temperature minimum of a more stoichiometric sample (T_c = 198 K) is below 350 cm^?1. Also, new absorption peaks are seen to develop below T_c at about 3700 cm^?1 and 3300 cm^?1 for the non- stoichiometric and stoichiometric-crystals respectively. The observed phenomena are related to the energy gaps which open up in the band structure below the phase transition temperature.     

Observation of electronic Raman transitions from the transition metal ions Ti3+ and V4+ highly diluted in α-Al2O3

α-Al₂O₃ : Ti³⁺ (300 mass ppm concentration) at 10 K shows two electronic Raman transitions at 38 cm^-1 and 109 cm^-1. The E symmetry of the scattering matrix agrees with the selection rules for transitions between the ground state B_{$\text{3}\text{2}$} and the E_{$\text{1}\text{2}$} of the ground state manifold ²t_2g.α-Al₂o₃ : V⁴⁺ shows two very weak electronic Raman transitions at about 30 cm^-1 and 56 cm^-1 respectively.     

The infrared spectrum of OH-compensated defect sites in C-doped MgO and CaO single crystals

The IR spectra of OH-compensated point defects in MgO (and CaO) single crystals of various purity grades were reinvestigated. Three distinct groups of IR bands appear in the O-H stretching region: A, B and C around 3550 cm^?1 (3650 cm^?1), 3300 cm^?1 (3450 cm^?1) and 3700cm^?1 (3750cm^?1). They are assigned as follows: band A to the fully compensated, band B to the half compensated and band C to the overcompensated cation vacancies, [O?V”_catH?]^×, [O?V”_cat], and [O?O?V”_catH?$\text{]}\text{?}$, respectively.Upon cooling to 80 K the band A shows a complex behavior partly due to the formation of Ha molecules by charge transfer and concommittant O^? formation: [? (H₂)”_cat?]^×. The O^? represent defect electrons or positive holes in the O^2? matrix.Bands A and B show a characteristic multiplet splitting which is caused by local lattice strains coming from carbon atoms on near-by interstitial position. The intensity ratios between the multiplet components remain constant regardless of temperature pretreatments up to 1470 K, but strong variations of the integral intensities are observed. These are caused by the highly mobile C atoms entering and leaving reversibly the cation vacancy sites as a function of temperature and of the quenching speed. When the C atoms push the H₂ molecules onto interstitial sites, an H-H stretching signal appears around 4150cm^?1.     

Crystal structure of and evidence of a lattice distortion in (Me2ø2P)(TCNQ)2

(Dimethyldiphenylphosphonium)⁺(7,7,8,8-tetracyanoquinodimethanide)^?₂ is monoclinic, space group C_c, with a = 32.01(2), b = 6.56(1), $\text{c = 15.72(2)}\text{A}\text{?}$, β = 107.4(8)°. The TCNQ's stack plane-to-plane in columns parallel to b with (i) a mean interplanar spacing of 3.28 Å along the conducting chains and (ii) an exocyclic bond to quinonoid ring overlap of adjacent molecules. The conductivity along b, the needle axis, varies as $\text{σ = σ}{}_0\text{exp}\text{(}\text{?E}{}_{\mathrm{a}}\text{kT}\text{)}$ where σ_{300 K} = 0.05 S cm^?1 and E_a = 0.20 eV (Diethyldiphenylphosphonium)⁺(7,7,8,8-tetracyanoquinodimethanide)^?₂ is similarly monoclinic, space group C_c, with a = 31.48(2), b = 6.51(1), $\text{c = 15.48(2)}\text{A}\text{?}$, β = 104.2(8)°. The conductivity at 300 K and activation energy, both determined along b, are 1–10 S cm^?1 and 0.05 eV respectively. There is evidence of a lattice distortion in the dimethyl analogue only.     

Assignment of lattice vibrations of lithium jodate from IR,Raman and NQR data

It is shown that calculation of the temperature dependence of the ¹²⁷J NQR frequency $\text{(±}\text{1}\text{2}\text{? ±}\text{3}\text{2}\text{)}$ on the basis of Bayer-Kushida theory allows one to interpret the IR and Raman spectra (ν < 350 cm^?1) of hexagonal crystal LiJO₃.     

Raman and mid-infrared spectroscopic study of the phase transitions in octafluoronaphthalene at elevated pressures

Raman and mid-infrared spectra of C₁₀F₈ have been obtained under hydrostatic pressures up to 17 kbar in a diamond anvil cell. The C₁₀F₈ I–II phase change, previously observed by neutron diffraction at about 0.8 kbar, has been confirmed. No evidence was found to support the existence of a furtt ier phase change between 4 and 6 kbar indicated by the neutron work, although this is certainly not precluded as the extra spectral features expected in this case are extremely small. The mode Grüneisen parameters, γ_i, allow a clear distinction between internal and external molecular modes, and scale roughly in accord with Zallen's relation γ_i$\text{\$}\text{?}$v_i^?2.     

Structure,vibrational study and conductivity of the trihydrated uranyl bis(dihydrogenophosphate): UO2(H2PO4)2·3H2O

The X-ray structure (293 K) of UO₂(H₂PO₄)₂·3H₂O has been refined (R = 0.062): M_r = 518g, space group: P2₁/c (Z = 4); $\text{a = 10.816(1)}\text{A}\text{?}$, $\text{b = 13.896(2)}\text{A}\text{?}$, $\text{c = 7.481(1)}\text{A}\text{?}$, β = 105.65(1)^°, $\text{V = 1082.7(2)}\text{A}\text{?}{}^3$; D_c = 3.17 Mg m^?3. The structure consists of infinite chains along the (101) axis with U atoms bridged by two H₂PO₄ groups. The U atom is surrounded by a pentagonal bipyramid of oxygen atoms, one of them being an equatorial water molecule. The cohesion between the chains is ensured by hydrogen bonds involving the two last water molecules. An assignment of IR and Raman bands with isotopic substitution spectra is proposed. A phase transition at 128 K was made evident by DSC and spectroscopy. The room-temperature phase is characterized by a high disorder of the OH bond orientation while in the low-temperature phase H₂O and POH species appear well oriented. The conductivity seems to occur by proton transfer and protonic-species rotation at the POH-water molecular interface between the chains. ac conductivity has been determined by means of the complex-impedance method ($\text{σ}{}_{\mathrm{<mtext>RT</mtext>}}\text{～ (3?12) × 10}{}^{\mathrm{?5}}\text{Ω}{}^{\mathrm{?1}}\text{cm}{}^{\mathrm{?1}}$; E ～ 0.20 eV).     

A monte-carlo/molecular dynamics study of the diffusional recombination kinetics of C(a) + O(a) → CO(g) on Pt(111)

The diffusion constants for C and O adsorbates on Pt(111) surfaces have been calculated with Monte-Carlo/Molecular Dynamics techniques. The diffusion constants are determined to be D_C(T)=(3.4 × 10^?3e^{$\text{?13156}\text{T}$})cm²s^?1 for carbon and D_O(T) = (1.5×10^?3 e^{$\text{?9089}\text{T}$}) cm² s^?1 for oxygen. Using a recently developed diffusion model for surface recombination kinetics an approximate upper bound to the recombination rate constant of C and O on Pt(111) to produce CO_(g) is found to be (9.4×10^?3 e^{$\text{?9089}\text{T}$}) cm² s^?1.     

Analysis of torsional splittings in the microwave spectra of dimethylether,CH3OCH3 and its isotopes,CD3OCH3 and CD3OCD3

The multiplet splitting patterns of microwave transitions in the ground state and the first two torsional excited states of CH₃OCH₃, CD₃OCD₃, and CD₃OCH₃ were analyzed in terms of the semirigid rotor models C_2vF-C_3vT-C_3vT and $\text{C}{}_3\text{F-}\text{C}{}_{\mathrm{3v}}\text{T-}\text{C}{}_{\mathrm{3v}}\text{T}\text{?}$. The following nonzero potential coefficients were obtained for CH₃OCH₃: V₃₀ = V₀₃ = 909.05 ± 0.49 cm^?1, V′₃₃ = 5.06 ± 1.60 cm^?1; for CD₃OCH₃: V₃₀(CD₃) = 897.18 ± 2.41 cm^?1, V₀₃(CH₃) = 910.45 ± 0.33 cm^?1; for CD₃OCD₃: V₃₀ = V₀₃ = 897.00 cm^?1. These results are compared to earlier microwave studies of these molecules.     

Analysis of the Raman spectrum of SF6

The Raman active fundamentals ν₁(A1g), ν₂(Eg), ν₅(F2g), and the overtone 2ν₆ of SF₆ have been investigated with a higher resolution and the band origins were estimated to be: ν₁ = 774.53 cm^?1, ν₂ = 643.35 cm^?1, ν₅ = 523.5 cm^?1, and 2ν₆ = 693.8 cm^?1. Raman and infrared data have been combined for estimation of several anharmonicity constants. The ν₆ fundamental frequency is calculated as 347.0 cm^?1. From the analysis of the ν₂ Raman band, the following rotational constants of both the ground and upper states have been calculated:

$\text{B}{}_0\text{= 0.09111 ± 0.00005}\text{cm}{}^{\mathrm{?1}}\text{; D}{}_0\text{= (0.16±0.08)10}{}^{\mathrm{?7}}\text{cm}{}^{\mathrm{?1}}$

;

$\text{B}{}_2\text{= 0.09116 ± 0.00005}\text{cm}{}^{\mathrm{?1}}\text{; D}{}_2\text{= (0.18±0.04)10}{}^{\mathrm{?7}}\text{cm}{}^{\mathrm{?1}}$

.     

A Raman scattering study of long-wavelength optical phonons in hexagonal ammonium fluoride single crystals

All the predicted Raman active translatory vibrations of wurtzite ammonium fluoride (space group C⁴_6v are observed and assigned on the basis of their polarization selections obtained with single crystals. The fundamental ammonium ion librations could not be detected, but a frequency of about 545 cm^?1 is deduced from the analysis of the observed second order Raman spectrum.The TO-LO splitting for the A₁ and E₁ polar phonons is a lot more important than the A₁ — E₁ splitting (125 cm^?1 compared to 1–3 cm^?1); thus, the effect of long-range electric forces strongly dominates over that of the anisotropy of the shortrange interatomic forces. Only very weak directional dispersion could be detected on the quasi-mode spectra. From the observed TO and LO frequencies, one evaluates ?₀ ? 3.95 in good agreement with dielectric experimental data.     

Optic-mode coupling in ferroelectric gadolinium molybdate

Separate measurements of the A₁(TO) and A₁(LO) Raman spectra of ferroelectric gadolinium molybdate at 80°K and above have elucidated the origin of the anomalous temperature dependence of the two lowest frequency lines in the A₁(TO) spectrum. The observed behavior is postulated to be the result of coupling among modes at 44.5, 51.5, and 83 cm^?1 (at 80°K). The 44.5 and 83 cm^?1 modes become the degenerate, soft zone-boundary modes of the paraelectric phase while the 51.5 cm^?1 mode changes to B₂ symmetry. The two lowest frequency lines are the same as those observed previously in i.r. absorption.     

Visible absorption and resonance Raman spectra of alkaline earth metal ozonides in argon and nitrogen matrices at 10 K

Optical and resonance Raman spectra of the reaction products of Mg, Ca, Sr, and Ba with ozone were observed in argon and nitrogen matrices. The visible spectra were characterized by strong, vibronically structured absorptions between 540 and 350 nm, and are assigned to the alkaline earth metal ozonides, $\text{A}{}^{\mathrm{+}}\text{O}{}_3{}^{\mathrm{?}}$. Vibrational analysis yielded ω₁′ and ω₁x₁ values of about 900 and 6 cm^?1, respectively, with only slight variation from metal to metal. Resonance Raman spectra consisted of a strong fundamental near 1020 cm^?1 and two overtones with decreasing intensity. Oxygen-18 substitution confirmed the vibrational assignments, which agree very well with the alkali metal ozonide spectra. These results suggest that the +1 oxidation state plays an important role in the chemistry of the alkaline earth metals under conditions where aggregation does not occur to favor the +2 state. A thorough search was made for absorptions due to the alkaline earth oxide species, but no bands were observed.     

Determination of A0 for CH335Cl and CH337Cl from the ν4 infrared and Raman bands

The ν₄ infrared and Raman bands of CH₃Cl were analyzed simultaneously. A direct fit yielded a complete set of constants for CH₃³⁵Cl, including A₀ = 5.20530 ± 0.00010 cm^?1 and D_K = (8.85 ± 0.13) × 10^?5cm^?1. For CH₃³⁷Cl an incomplete set of constants was obtained from the infrared band, and A₀ = 5.2182 ± 0.0010 cm^?1 was estimated by curve fitting of the Raman spectrum. The resulting equilibrium structure is $\text{r(}\text{CH) = 1.0854 ± 0.0005}\text{A}\text{?}$, $\text{r(}\text{CCl) = 1.7760 ± 0.0003}\text{A}\text{?}$, and <(HCH) = 110°.35 ± 0°.05.     

Single vibronic level fluorescence spectra of sulfur dioxide

Single vibronic level fluorescence spectra of sulfur dioxide have been recorded throughout most of the region corresponding to the $\text{A}\text{?}\text{-}\text{X}\text{?}$ absorption. These spectra show progressions in the symmetric stretching mode of at least five members. Twelve origins between 30 972 and 31 776 cm^?1 show remarkably similar Franck-Condon (FC) patterns for this progression. Seven origins between 31 840 and 32 257 cm^?1 show another distinct FC pattern. This behavior is repeated for three more regions of excitation, each with a different distinct FC pattern and each containing numerous origins spread throughout a region of about 700 cm^?1. The progressions in the symmetric bending mode are essentially absent in the lowest energy excitation spectra and then slowly increase in length as the excitation energy increases. There is limited activity in both even and odd quanta of the antisymmetric stretching mode. These results are interpreted in terms of the levels of a zero-order ¹B₁ electronic state (with zero-order origin at around 31 240 cm^?1) that are very strongly vibronically coupled to many more ¹A₂ levels (with lower energy zero-order origin). The bulk of the emission is what would be expected from the zero-order ¹B₁ levels spread among the ¹A₂ levels.     

A new ferroelectric compound: Methylammonium trichloromercurate (CH3NH3HgCl3)

Measurements of the dielectric constants revealed a ferro- to paraelectric transition in methylammonium trichloromercurate (CH₃NH₃HgCl₃). Thermal analysis by differential scanning calorimetry indicates a transition temperature of Tc ≈ 60°C. The structures of both phases were determined from single crystal X-ray measurements. The ferroelectric phase crystallizes at room temperature in the polar trigonal space group $\text{P}\text{3}{}_2\text{(a = b =}\text{7.8117(3)}\text{, c =}\text{9.826(3)}\text{A}\text{?}\text{, Z =}\text{3}\text{)}$. The refinement of the ferroelectric structure included the fractional contribution of the two domains present. The paraelectric phase has monoclinic symmetry (space group C2 with $\text{a =}\text{13.816(2)}\text{, b =}\text{7.880(1)}\text{, c =}\text{9.734(3)}\text{A}\text{?}\text{, β =}\text{90.49(5)°}\text{, Z =}\text{6}\text{)}$ and contains an almost completely disordered methylammonium group while order with pronounced thermal motion is observed in the ferroelectric phase.     

Electron diffraction and infrared study of the semimetallic layered compound Ti1−xVxSe2

The crystals of the system Ti_1?xV_xSe₂ (C ≤ x ≤ 0.05) undergo a second order structural phase transition. Electron diffraction studies show that the transition temperature decreases with progressive V-doping. The phase transition considerably affects the infrared reflectivity, measured at 300 and 77 K in the spectral range 40 cm^?1 to 4000 cm^?1.The presence of free carriers and the existence of optical infrared active E_u phonon modes $\text{(}\text{E}\text{⊥}\text{c}\text{)}$ confer their characteristic appearance to the spectra. At room temperature one phonon structure is measured at 143 cm^?1. At 77 K a new series of phonon peaks appears up to a V-concentration of 5 % as a direct consequence of superlattice formation.At room temperature the plasma-edge shifts towards higher frequencies as the vanadium concentration increases. This effect is caused by a large increase of $\text{N}\text{m}{}^1$, associated with the mixing of impurities. It is indicative of the small density of states at the Fermi level in semimetallic TiSe₂. Our results suggest a phase transition driven by lattice dynamical effects.