Emission spectra of supersonically cooled chloroacetylene cations

The ā²Π_Ω → X?²Π_Ω, Ω = $\text{3}\text{2}$, $\text{1}\text{2}$ emission spectra of rotationally cooled chloro- and deuterochloro-acetylene cations have been obtained by electron-impact ionisation of a seeded helium supersonic free jet. The resultant spectral improvements lead to the identification of the spin-orbit components and isotope splittings and to a vibrational assignment of the prominent bands. The vibrational frequencies could be determined to within ±1 cm^?1 for many of the fundamentals for the cations in the X?²Π_Ω and ā²Π_Ω electronic states.     

Gradient expansion of the atomic kinetic energy functional

It is demonstrated that the ground-state atomic kinetic energy functional T[?], where ? is the electron density, can be computed to surprising accuracy from the truncated gradient expansion: T[?] = + T₂[?] + T₄[?], with T_o[?] = $\text{3}\text{10}$(3π²)$\text{2}\text{3}$ ∫ ?$\text{5}\text{3}$ d_τ, T₂ [?] = $\text{1}\text{72}$ ∫ (??)²?^?1 d_τ, and T₄ [?] given by the formula of Hodges. Calculations of T₀, T₂ and T₄ are reported for He with ? both the Hartree—Fock and a very accurate density, and for Ne, Ar and Kr with ? the Hartree—Fock density. For Kr, T₀ + T₂ + T₄ is within 0.3% of the exact Hartree—Fock T, with T₂/T₀ = 0.05, T₄/T₂ = 0.17.     

The crystal structure of vanadium ditelluride,V1+xTe2

Vanadium ditelluride, V_1.04Te₂, has a Cd(OH)₂-type structure with unit cell dimensions a_h = 3.638 Å and c_h = 6.582 Å above the transition temperature T_t of 482 K. Below T_t the structure is monoclinic, space group $\text{C2}\text{m}$, with cell dimensions a_m = 18.984 Å(≈3a_h√3), b_m = 3.5947 Å (≈a_h), c_m = 9.069 Å (≈√(3a²_h + c²_h)), β = 134.62°. This low-temperature form is isostructural with NbTe₂ and TaTe₂ (which do not show a phase transition); the vanadium atoms form double zigzag chains with VV distances of 3.316 Å, which distort the Te lattice. Complex diffraction patterns were observed due to the simultaneous occurrence of the distortion of the Cd(OH)₂-type structure of vanadium ditelluride in three equivalent directions. Similar patterns were found for the Nb and Ta ditellurides.     

Neutron and X-ray diffraction study on polymorphism in lithium orthotantalate,Li3TaO4

The structures of the low-and high-temperature modifications of lithium orthotantalate, Li₃TaO₄, have been determined by neutron and X-ray diffraction methods. The low-temperature, or β, phase has symmetry $\text{C2}\text{c}$ and lattice parameters a₁ = 8.500(3), b₁ = 8.500(3), c₁ = 9.344(3)Å, and β = 117.05(2)°. The high-temperature, or α, phase has symmetry P2 and lattice parameters a_h = 6.018(1), b_h = 5.995(1), c_h = 12.865(2)Å, and β_h = 103.53(2)°. Both structures are ordered. The β-phase has a rock salt-type structure with a 3 : 1 ordering of the Li⁺ and Ta⁵⁺ ions. Its structure can be generated from the low-temperature modification by means of a complex pattern of shifts of the Ta⁵⁺ ions.     

Theory of v2 (AH) vibration IR bandshapes of weak and moderately strong hydrogen-bonded complexes in liquids

A quasicrystalline model of liquids is used to calculate the ν_s(AH) vibration IR absorption band profile of a hydrogen-bonded complex in solution. We consider relatively broad bands with the half-widths Γ obeying the relation Γ ? Ω_m, where Ω_m is the mean frequency of the intermolecular vibrations in the medium surrounding the complex. No restrictions, however, are imposed on the relative magnitudes of Γ and Ω, the ν_σ(AH … B) oscillator frequency. The system is also assumed to be far from Fermi resonances. In the case when Ω exceeds Ω_m, the $\text{A}$ … $\text{B}$ motion is separated in coherent and stochastic parts. The band profile is represented as an envelope of the equidistant sequence of combination bands (separated by ≈ Ω) arisen from the coherent part and broadened by the stochastic component of the $\text{A}$ … $\text{B}$ motion. The band contour is described in terms of the internal characteristics of the hydrogen-bonded complex only when the interaction of the ν_σ(AH … B) oscillator with the medium is weak (this can occur only if Ω ? Ω_m), the band is featureless and Γ ? Ω. The weakness of the interaction, however, may be incompatible with the requirement that the $\text{A}$ … $\text{B}$ motion is stochastic and, correspondingly, the bandshape is featureless. We formulate for this case the condition for combination bands to be spectrally unresolved. If Ω ? Ω_m, the interaction of the ν_σ (AH … B) oscillator with the environment is necessarily strong. Accordingly, the bandshape depends then not only on the intrinsic characteristics of the complex but also on the properties of the solvent. The case Γ ≈ Ω corresponds to the partial motional narrowing of the band. In this regime the H → D substitution effect and the change of the band half-width with temperature become more pronounced than in the systems with quasistatic (Γ ? Ω, Ω_m) band profiles.     

Molecular predissociation dynamics revealed through multiphoton ionisation spectroscopy. I. The C1B1 states of H2O and D2O

The $\text{C}$¹B₁ states of H₂O and D₂O have been observed by means of three photon absorption (four photon ionisation) spectroscopy. Differences between the experimentally observed 3 + 1 multiphoton ionisation spectrum and that predicted by the appropriate asymmetric-top three-photon line-strength theory are attributed to $\text{C}$ state predissociation. Two separate predissociation mechanisms have been identified, one (heterogeneous) relying on a-axis parent molecular rotation to couple the bound B₁ state to an unbound state of A₁ electronic symmetry, the other (homogeneous) involving a second, dissociative excited electronic state of B₁ symmetry. Having established the detailed $\text{C}$ state predissociation dynamics, two photon absorption spectra of H₂O and D₂O ($\text{C}$ ← $\text{X}$) can be predicted accurately: studies of individual quantum-state-selected photofragmentation processes from H₂O($\text{C}$) are proposed.     

A study of polytypism in AgIn5Se8 by combined electron microscopy techniques

Three different polytypes are found to exist in AgIn₅Se₈. They have been studied by means of conventional electron microscopy and diffraction as well as by high-resolution microscopy. The three different structures have tetragonal symmetry and can be derived from each other by means of periodic antiphase boundaries; they correspond to $\text{c}\text{a}\text{= 4,}\text{c}\text{a}\text{= 2}$, and $\text{c}\text{a}\text{= 1}$, respectively. Regions of $\text{c}\text{a}\text{= 4}$ often occur as microsyntactic intergrowths into $\text{c}\text{a}\text{= 2}$ areas, and a large number of nonperiodic antiphase boundaries also occur. After fast cooling from above T_c a transition state characterized by the presence of diffuse intensity has been observed and analyzed.     

Heat capacity of pure and doped V2O3 single crystals

Heat capacities have been measured for single crystals of V₂O₃, either pure or doped with 1 and 1.4 mole% Cr₂O₃ and Al₂O₃ over the temperature range 100–700°K. V₂O₃ undergoes a fairly sharp transition at low temperatures (～170°K) but fails to exhibit any thermal anomaly above 300°K. The thermal behavior of (M_xV_1?x)₂O₃, M = Cr, Al, is manifested by two transitions: one at low temperatures, 170–180°K for x = 0.01 and 180–190°K for x = 0.014, and the other at high temperatures. For x = 0.01, the high-temperature (HT) anomaly extended over the range 325–345°K (Cr-doped V₂O₃) and 345–365°K (Al-doped V₂O₃), respectively. The corresponding ranges for x = 0.014 were found to be 260–280°K and 270–290°K, respectively. Further, the HT anomaly was characterized by a large hysteresis (～50°K). The values of lattice heat capacity of pure and doped V₂O₃ were, however, found to be almost the same and could be empirically represented by the Debye (D)?Einstein (E) function $\text{D}\text{(}\text{580}\text{T}\text{) + 4}\text{E}\text{(}\text{θ}\text{T}\text{)}$ with θ values 430°K (T = 100–230°K) and 465°K (T > 230°K), respectively. Further, the enthalpy change ΔH associated with the HT anomaly in doped V₂O₃ (80 ≤ ΔH ≤ 510 J/mole) was 5–10 times smaller than the ΔH corresponding to the lower-temperature transition. The results cited here appear incompatible with the Mott transition model that has been invoked to explain the HT anomaly.     

Phase transition in the family LaxBi4−xTi3O12: In relation to lattice symmetry and distortion

The ferroelectric phase transition in the family La_xBi_4?xTi₃O₁₂ was investigated by X-ray diffractometry and differential scanning calorimetry. The crystal symmetry is orthorhombic in the range of 1 > x ≥ 0 and tetragonal in x ? 1. It was found that the shift of the phase-transition temperature is closely related to crystallographic symmetry and lattice distortion. (1) As the value of x increases, the ratio of lattice parameters, $\text{a}\text{b}$, decreases toward 1. (2) In the range of 1 > x ≥ 0, the lattice distortion increases with increasing x; just before x exceeds about 1, the distortion reaches a maximum. (3) As x exceeds about 1, the distortion decreases distinctively. (4) In the orthorhombic region, the phase-transition temperature decreases with increasing x. (5) In the tetragonal region, the transition does not occur. (6) The relation of transition temperature T_c to x is represented by a nonlinear function.     

Determination of optical properties of hexagonal lithium iodate crystal by use of NQR and IR spectroscopy

The NQR Zeeman effect of ¹²⁷I (± $\text{1}\text{2}$ ←→ ± $\text{3}\text{2}$ transition) for the LiIO₃ crystal of hexagonal modification has been investigated, and the EFTG asymmetry parameter for nuclei of ¹²⁷I determined. Measurements of optical properties of the z-cut crystal in polarized light within the region of stretching vibrations and their overtones for IO^?₃ revealed that transmission (reflection) depends on the direction of the incident light wave electric vector. The results obtained indicate that crystals of LiIO₃ grown from aqueous solutions show anomalous biaxiality.     

Observation of a possible pure electric quadrupole transition in solid Cs2NaSmCl6

A no-phonon transition has been observed in Cs₂NaSmCl₆ at 6355 cm^?1. This transition is assigned, in octahedral symmetry, as E″_u(⁶H_{$\text{5}\text{2}$}) → E'_u(⁶F_{$\text{1}\text{2}$}) and is proposed to be of pure electric quadrupole origin. A comparison between the experimental and calculated intensity and the orientation-dependent intensity of an associated vibronic transition lend support to this assignment.     

Refinement of β-LiIO3 crystal structure by use of zeeman effect on the NQR line and ir-reflection spectra

The NQR Zeeman effect of ¹²⁷I quadrupole resonance (±$\text{1}\text{2}$ ↓ ±$\text{3}\text{2}$ transition) and the polarized IR spectra of a single crystal of β-LiIO₃ have been studied. The z-axes of the EFG orientation in the unit cell were determined; the EFG asymmetry parameter for the ¹²⁷I nuclei was refined giving η = 0.027 ± 0.003 at 300 K for β-LiIO₃. The dichroic ratio in the (100) crystal plane over the I-O stretching vibration region has been measured from polarized spectra and calculated on the basis of an “oriented gas” model by the use of refined structural data. Comparison of some spectral, structural and quantum-chemical characteristics of both β- and α-modifications of LiIO₃ crystal has been made.     

Electrical properties of the CuCr2O4 spinel catalyst

Electrical resistivity of CuCr₂O₄ spinel obtained by a coprecipitation method was measured at various temperatures from 350 to 923K in air. Oxidation of its surface chromium ions at various temperatures was determined by an iodometric method. The temperature dependence of resistivity and the presence of higher-valent chromium ions at higher temperatures indicated CuCr₂O₄ to be an extrinsic semiconductor. Log ? vs $\text{1}\text{T}$ plots yielded straight lines in the whole temperature range with two breaks, one around 550K and the other around 730K. The first break was attributed to the saturation of the surface with higher-valent chromium, while the second break was attributed to tetragonal-to-cubic phase transition in CuCr₂O₄. Log ? vs $\text{1}\text{T}$ plots obtained while cooling exhibited hysteresis near the second break, confirming this break to be due to a first-order diffusionless transition.     

The influence of the orientation of the NO molecule upon the chemiluminescent reaction NO+O3→NO2*+O2

A beam of state-selected NO molecules (J = Ω = $\text{3}\text{2}$) has been produced by an electrostatic hexapole and has been collided with O₃ molecules in a scattering chamber. The E-field dependence of the chemiluminescent cross section, σ_hr, has been investigated and resulted in the determination of the M-dependence of σ_hr: σ_hr (M)/σ₀ = 1.192±0.009, 0.0848±0.015, 1.177±0.015, 0.783±0.009 for M = $\text{3}\text{2}$, $\text{1}\text{2}$, $\text{?1}\text{2}$ and $\text{?3}\text{2}$, respectively. Application of the Legendre expansion technique and the density matrix formalism provided a deconvoluted σ_hr(γ), for a single angle of attack γ of the NO axis, expressed in simple model functions with adjustable parameters. From this analysis it is concluded that chemiluminescence only occurs when cos γ ≈ 1, the “end-on-head” orientation of NO yielding ≈ 30% of all collected light, and when cos γ ≈ ?0.275, the “broad-side-tail” orientation of NO yielding the remaining 70%. The steric factors belonging to these reactive orientations have been estimated and are S₁ = 0.25±0.07 and S₂ = 0.40±0.09, respectively. The observed dependence of σ_hr has been confronted with the rules of Woodward and Hoffman. Although there are indeed two symmetries (bpl and cpl) correlating the electron orbitals of the reactants and the products, these rules do not lead to an explanation of the steric effects of the NO+O₃ reaction.     

Infrared high temperature spectra of aluminium chloride and related species

Isothermal cells of nickel with diamon windows were used to study various melts and vapours by infrared emission, transmission and reflectance techniques in the 860 to 300 K range with an evacuable Fourier transform spectrometer.IR vapour spectra of AlX₃ (X = Cl, Br, I) and GaCl₃ in transmission and emission were measured between 700 and 50 cm^?1. A comparable signal/noise ratio between the transmission and emission spectra was obtained above 200 cm^?1, below 200 cm^?1 the transmission spectra had better quality. The dimer and monemer spectra were assigned in terms of $\text{D}$_2h and $\text{D}$_3h symmetry, respectively, and compared with earlier Raman and IR matrix isolation data.Emission spectra of chloroaluminates AlkAlCl₄ (Alk = Li, Na, K, Rb, Cs) were recorded as melts between 1500 and 50 cm^?1. Increasing distortion of the tetrahedral AlCl^?₄ ion in the series Cs<Rb<K<Na<Li was observed. Emission spectra of AlkAl₂Cl₇ (Alk = Li, Na, K, Cs) indicate $\text{D}$_3d symmetry for Al₂Cl^?₇ with a linear Al-Cl-Al bridge as proposed from earlier Raman data. As a demonstration of reflectance technique an IR spectrum of ZnAl₂Cl₈ at ambient temperature is presented.     

High pressure and high temperature investigations in the system MgOSiO2H2O

The system MgOSiO₂H₂O was investigated at pressures between 40 and 95 kbar and at temperatures between 500 and 1400°C. The reaction products were examined by X-ray, optical and thermal analysis techniques and the density of phase A discovered by Ringwood and Major was also measured. It was found that phase A was hydrated and its chemical formula was H₆Mg₇Si₂O₁₄. When the $\text{Mg}\text{Si}$ ratio of the system is 2, phase A + clinoenstatite, and forsterite are stable at temperatures lower and higher than a boundary curve T (°C) = 10P (kbar), respectively. When the $\text{Mg}\text{Si}$ ratio of the system is 3, phase A + phase D (which is completely different from the phases, A, B and C discovered by Ringwood and Major, and any other known phases of magnesium silicate) and phase D + brucite are stable at temperatures lower and higher than a boundary curve T(°C) = 10P (kbar) + 200. Phase A has approximately an hexagonal symmetry and the space group and the lattice parameters are determined as P6₃ or $\text{P6}{}_3\text{m}$ and a = 7.866(2) Å and c = 9.600(3) Å, respectively. The measured density is 2.96 ± 0.02 g/cm³. The optical observations show that phase A is biaxial positive crystal with refractive indices α = 1.638 ± 0.001, β = 1.640 ± 0.002, and γ = 1.649 ± 0.001. Some interpretation is given on the inconsistency between the symmetry determined by the X-ray diffraction and the optical observation. The new phase D belongs to the space group $\text{P2}{}_1\text{c}$ with lattice parameters a = 7.914(2)Å, b = 4.752(1) Å, c = 10.350(2) Å and β = 108.71(5)° and is a biaxial crystal with refractive indices α = 1.630 ± 0.002, β = 1.642 ± 0.002 and γ = 1.658 ± 0.001.     

Computer plots of HOH normal modes depending on time

The combination of the antisymmetric and symmetric stretching vibrations of water is a decoupled OH vibration. It means the X₁₃ anharmonicity constant of HOH must be related with the X₃₃ anharmonicity constant of HOD. It is found that $\text{1}\text{2}$X₁₃(HOH)= X₃₃(DOH) = X(OH). Instead of the usual condition X_ik = 0 for i > k a new definition will be given for the anharmonicity constants: $\text{X}$_ik = $\text{X}$_ki. The X values of other molecules were compared with each other and it follows the general rule for a symmetric molecule m-M-m with m ? M: $\text{X}$₁₃ (mMm) = $\text{X}$₃₁ (mMm) = X (Mm).Computer plots of normal modes of the ν₁ + ν₃ combination depending on time show the rotation of the dipole moment derivatives vector. It is strongly different for H₂O and HOD and explains the different band intensities. We expect higher band intensities and X₁₃ values using IR light with rotating electric field vector.     

Electronic raman transition from an optically pumped excited state

From the intensity behaviour of a 29 cm^?1 Raman shift of α-Al₂O₃:Cr³⁺ as a function of the incident power, it is concluded that the shift is due to an electronic Raman transition between the components of the excited state ²E. Population of the excited states is obtained through a pumping mechanism induced by the laser radiation λ_$\text{o}$ = 514.5 nm which at the same time serves as a Raman probe.     

Phase diagram and some physical properties of V2O3+x1 (0 ? x ? 0.080)

The magnetic and electric properties of V₂O_3+x were investigated by measurements of magnetic susceptibility, electrical resistivity, magnetotorque, Mössbauer of doped ⁵⁷Fe, and NMR of ⁵¹V, and the results were compared with those of the (V_1?xTi_x)₂O₃ system or highly pressured V₂O₃. The results obtained are as follows: (1) The metallic state shows an antiferromagnetic ordering at T_N (x). The value of T_N for metallic V₂O₃, obtained by interpolation to x = 0, shows the coincidence between V₂O_3+x and the (V_1?xTi_x)₂O₃ system. (2) Magnetic susceptibility of V₂O_3+x is expressed as χ_M(V₂O_3+x) = (1?x)χ_M(V³⁺) + xχ_M(V⁴⁺). χ_M(V⁴⁺) obeys the Curie-Weiss law $\text{(χ}{}_{\mathrm{<mtext>M</mtext>}}\text{(}\text{V}{}^{\mathrm{4+}}\text{) =}\text{0.77}\text{T}\text{+ 17)}$. (3) In the insulating phase, the electrical resistivity ? is expressed as a common equation: $\text{? = 10}{}^{\mathrm{?1.8}}\text{exp}\text{(}\text{E}\text{kT}\text{)}$. This implies that the substitution of Ti or nonstoichiometry (V⁺⁴ + metal vacancies) has little influence on the carrier mobility (or bandwidth). (4) There is a critical length in the c-axis (? 14.01 Å) where the metal-insulator transition takes place. This suggests that the length of the c-axis plays an important role in the metal-insulator transition of V₂O₃-related compounds.