3-Naphthyl-4-Quinazolone Infrared and Nuclear Magnetic Resonance Band Assignments

Abstract

The ir and nmr spectra of 24 3-naphthyl-4-quinazolones were examined. There are three principal ir bands in the 1500 and 1705 cm^?1 region of the spectra. The first at 1685–1705 cm^?1 is assigned to the tertiary amide carbonyl (ArCONR₂), the second at 1593–1645 cm^?1 to the anil chromophore (ArN=C-N) and the third to the naphthalene ring at 1600 cm^?1. The nmr band assignments are straight forward.     

ESR evidence of a low-temperature phase transition in Na2SeO4

Abstract

ESR investigations of gamma-irradiated sodium selenate in powder form indicates a number of paramagnetic species as SeO^? ₂, SeO^? ₃, and SeO^? ₄, identified on the basis of their g-tensors. The appearance of a new ESR line at g = 2.0260 attributed to the SeO^? ₄ radical indicates a possible structural phase transition at 165 K in Na₂SeO₄.     

Investigation of Nd2CuO4 crystal structure at high pressure by neutron diffraction

Abstract

The crystal structure of Nd₂CuO₄ has been studied by neutron diffraction at pressure up to 5 Gpa. The volume compressibility value was determined as 5·6·10^?3/Gpa. The decrease of positional parameter of neodymium at high pressure has been observed. This structural change is explained by pressure induced neodymium ions charge increase.     

Normal Unenhanced Raman Spectra of CO and CH4 Adsorbed on Cobalt(poly)

Abstract

Normal unenhanced Raman spectra (NURS) of low-polarizability CO molecules were observed for the first time on cobalt at R. T. and residual gas pressure. We assign five bands observed between 2030–2130 cm^?1 to linear chemisorbed CO species, while those observed between 1840–2010 cm^?1 have been ascribed to the 2-fold chemisorbed species. The three bands observed between 1740–1830 cm^?1 we believe are due to the 3-fold species. The corresponding fourteen Co-C stretches were observed and assigned. A model based upon electron backdonation is proposed for each of the three structures. NURS were also observed at R. T. for physisorbed CH₄ and assignments are made to the four frequencies of CH_4.     

IR Spectra of Be(IO3)2.nH2O (n = 4, O) and of the Deuterated Analogue

Abstract

The compounds of beryllium - Be(IO₃)₂.4H₂O, its deuterated analogue and Be(IO₃)₂ were studied by IR-spectroscopy over the range of 200 to 4000 cm^?1.     

Superionic phase transition in (NH4)2SeO4·2NH4HSeO4 single crystal at 378 K

Abstract

DTA, structural and electric conductivity investigations were made for (NH₄)₄H₂(SeO₄)₃ single crystals. A high-temperature phase transition at 378 K to a superionic phase was found. The phase is characterized by a high electrical conductivity (～4.10^?3 Ω^?1 cm^?1) and a low activation energy (0.11 eV).     

Semiconducting properties of refractory oxides systems

Abstract

The electrical conductivity and thermoelectric power of pure and doped oxides system La₂O₃-Cr₂O₃-Al₂O₃ were investigated. Only single phase was observed in the compositions studied (20 atom fraction of aluminium).

The conductivity increases with increasing chromium content in the range of compositions studied, the values ranging from 10^?4 (ω-cm)^?1 to 1. 2 × 10^?1(ω-cm)^?1. In the case of samples doped with calcium (0. 01) the corresponding values range from 2 × 10^?1 (ω-cm)^?1 to 1. 67(ω-cm)^?1. The significance of the results has been discussed.     

Computer Resolution and Franck-Condon Analysis of the Electronic Absorption Spectrum of KMnO4 in Water

Abstract

The electronic absorptíon spectrum of KMnO₄ in water solution was analyzed. The spectral contour was resolved into component bands and then Franck-Condon approach was applied. In the investigated range of 13000–48000 cm^?1 a presence of three structureless and of two vibronic strong bands was stated. The change in the Mn-O equilibrium bond length was found to be 10.5pm for 2e·1t₁ transition (vibronic band about 18000cm^?1) and to be 16pm for the 2e·3t₂ transition (vibronic band about. 30000cm_?1). The appropriate wavenumber of the vibrational mode in these excited electronic states was found to be 735cm^?1 and about 780cm^?1, respectively. The ground electronic state wavenumber of the totally symmetric vibrational mode was fitted to be equal to 828cm^?1. Details of the proposed method of computer elaboration of electronic spectra with vibrational structure were discussed.

Electronic absorption spectra of some inorganic comppunds consist of a number of strongly overlapped bands due to their vibronic structure.^1–5 A detailed analysis of spectral contours of such compounds provides some useful information about their structure in both ground excited electronic states.

The electronic spectrum of permanganate ion is the typical example of vibronic spectra.¹ The main part of the past works based on the analysis of permanganate ion spectra in low temperatures and different polarizations. In such conditions the vibronic structure is rather good resolved and can be effectively studies.^1,3,6 Spectra of solutions as a rule are relatively poor resolved so their analysis has to be more sophisticated.

The main purpose of this work is a presentation of a new computer method for an effective study of vibronic spectra of solutions. This method has been applied to the electronic absorption spectrum of KMnO₄ in water. The method allowed us to fit the geometric parameters of spectral contour, to establish the origins and parameters of two progressions in the UV/VIS range as well as to calculate the changes in the Mn-0 equilibrium bond lengths and vibrational energy resulting from the electronic excitations of the soluted permanganate ion.     

Laser Raman Spectra of Crystalline Chloromercurate(II) Complexes

Abstract

The laser Raman spectra of crystalline [(CH₃)₄N] HgCl₃ and [(CH₃)₄N]₂HgCl₄ have been studied in the 400–20 cm^?1 region. All expected Raman active modes for the HgCl₃ ^? and HgCl₄ ^?2 ions are observed and assignments of the vibrational frequencies are made in relation to the structure of the anions.     

An Investigation of the Digitized Raman Band Profiles of Aqueous Mg(ClO4)2 - NaSCN Solutions

Abstract

Raman spectra, together with factor analysis and band deconvolution procedure, have been used to study formation of magnesium thiocyanate complexes in aqueous solutions at ambient and elevated temperatures. The total salt concentration in solutions, containing different mole ratio of Mg²⁺ to SCN, varied between 3.4 and 7.5 mol dm^?3. Factor analyses indicated that two linearly independent scattering components in the band envelopes, recorded in the V₁ and v₃ stretching regions of SCN, for all solutions with total salt concentration of 3.4 mol dm^?3. The appearance of a pseudo-isosbestic point in the area normalized spectra supported this result, as well as the baud resolution procedure. The latter revealed the third scattering component in the spectra of solutions with total salt concentration above 3.5 mol dm^?3 Resolved components have been assigned to the free thiocyanate, the 1:1 and 1:2 magnesium thiocyanate complexes. The equilibrium constant K_c of the 1:1 complex is of an order of 10^?1 mol dm^?3.     

Luminescence spectroscopy of high-energy 4f 11 levels of Er3+ in fluorides

The 4f¹¹ energy levels of Er³⁺ in LiYF₄ in the spectral region 39000–65000 cm^?1 have been studied. The agreement between experimental energy levels, obtained from luminescence excitation spectra, and calculated energy levels is good. Luminescence originating from high-lying energy levels has been investigated. Emission from the states ⁴D_1/2 (～47 200cm^?1), ²F(2)_7/2 (～54700cm^?1) and ²F(2)_5/2 (～63 300cm^?1) is observed. ²F(2)_5/2 emission occurs for Er³⁺ in LaF₃, where the ²F(2)_5/2 level is situated just below the lowest 4f¹⁰5d state, but also for Er³⁺ in LiYF₄, where it lies in between the two lowest 4f¹⁰5d states.     

Pressure-induced closure of the jahn-teller distortion in Rb2CuCl4(H2O)2

This work investigates the pressure-induced variation of the local structure around Cu²⁺ as well as the crystal structure in Rb₂CuCl₄(H₂O)₂ through XAS and XRD techniques. The application of pressure induces a structural change in the Jahn-Teller (JT) [Formula: See Text] complex from axially elongated to compressed. This change leads to the closing of the 2D JT distortion related to the four in-plane Cl^? ligands, which are responsible for the antiferrodistortive structure displayed by the crystal. It is shown that the presence of water ligands enhances a JT release. Their associated axial ligand-field favours the occurrence of such a local structural transition below the metallization pressure. The results are compared with recent pressure experiments on A₂CuCl₄ systems.     

Infrared Spectra of the Copper(II), Nickel(II) and Palladium(II) Complexes of 4-amino-3-pentene-2-one

Abstract

The infrared spectra of the metal complexes of 4-amino-3-pentene-2-one were measured from 4000 - 20 cm^?1. The absorption bands were assigned by comparison to other similar molecules: The Cu(II) complex of 4-methylamino-3-pentene-2-one, and complexes of acetylacetone. Force constants for the molecules were calculated using the A_xsm matrix method. The spectra were measured at 298^oK and 77^oK.     

Mößbauereffekt in FeCl2, FeSO4 und FeSO4 · 7 H2O

Mößbauereffect measurements were performed with FeCl₂, FeSO₄ and FeSO₄ · 7 H₂O in the temperature range between 5 and 300 ?K. The quadrupole splittings at 5 ?K were determined to be (1.300±0.027) mm/sec, (3.650±0.053) mm/sec, and (3.350±0.053) mm/sec respectively. From the temperature dependence of the quadrupole splittings it follows that in FeCl₂ the energy of the excited 3d-electron-level isδ=150 cm^?1, in FeSO₄ δ ₁=360 cm^?1 andδ ₂=1680 cm^?1 and in FeSO₄ · 7 H₂Oδ ₁=480 cm^?1 andδ ₂=1300 cm^?1. The magnitudes of the magnetic field at the iron nucleus at 5 ?K are (202±8) kOe for FeSO₄ and (0±4) kOe for FeCl₂.     

Phonons and magnetic order in ferromagnetic CdCr2Se4 and CdCr2S4

Measurements are reported of the Raman effect on single crystal ferromagnetic CdCr₂Se₄ and CdCr₂S₄ as a function of temperature. The lines observed at 158 cm^?1, 172 cm^?1 and 241 cm^?1 for CdCr₂Se₄ and 257 cm^?1, 281 cm^?1 and 396 cm^?1 for CdCr₂S₄ have been identified as due toГ ₁₂ ⁺ ,Г ₂₅ ⁺ andГ ₁ ⁺ phonons, respectively. Certain lines ofГ ₁ ⁺ orГ ₂₅ ⁺ symmetry, observed in both materials, show a temperature dependence of the intensity which resembles the behaviour of the spin correlation function. Some of these lines also exhibit a symmetry change at the Curie point. A group theoretical analysis of the eigenvectors of the Raman active modes is given. The results are interpreted in terms of a model proposed by Baltensperger which involves the ion position dependence of the magnetic exchange interaction in order to couple spin system and phonons. The weak frequency shift of the lines, which occurs predominantly in the ordered state, is interpreted in terms of the same model.     

High resolution infrared spectrum of the ν4 band of DCCF

The bending vibration-rotation band ν₄ of DCCF was studied. The measurements were carried out with a Fourier spectrometer at a resolution of about 0.03 cm^?1. The constants B₀=0.29141(1)cm^?1, α₄=?5.02(2)×10^?4cm^?1, q₄=4.52(3)×10^?4cm^?1, and D₀=9.2(4)×10^?8cm^?1 were derived. The rotational analysis of the “hot” bands 2ν₄(Δ) ← ν₄(II) and 2ν₄(Σ⁺) ← ν₄(II) was performed. In addition, the “hot” bands ν₄ + ν₅ ← ν₅ were assigned. A set of vibrational constants involved was derived.     

Infrared transitions of C2D6 from v 4 to the interacting system v 4+ v 6, v 4+ v8, v 3+ 2v 4: rotational analysis,and torsional splitting in the v 3+ 2v 4 and v 3+ v 4 states

The hot infrared transitions of C₂D₆ from the υ₄(A_1u ) to the υ₄ + υ₆(A_2g ) and υ₄ + υ₈(E _g ) vibrational states, observed from 960 to 1180 cm^?1, have been rotationally analysed on a high-resolution Fourier transform spectrum (full width at half-maximum about 0·0030 cm^?1). The vibration-rotation interactions affecting the upper vibrational states are very similar to those of the corresponding cold system. A strong x,y Coriolis interaction between υ₄ + υ₆ and υ₄ + υ₈, with K-level crossing, generates large displacements of the rotational components of both vibrational states, tuning them to additional local resonances in several spectral regions. Thus l resonances with Δl = ±2, Δk = ±1 occur within υ₄ + υ₈. A x,y Coriolis-type resonance between υ₄ + υ₈(?l,K ? 1) and υ₃ + 2υ₄(K) occurs at K = 11,12,13, and a further coupling of υ₄ + υ₈(+l,K + 1) and υ₃ + 2υ₄(K + 3) is most effective at K = 11 and 12. These resonances induce torsional splittings on the perturbed levels of υ₄ + υ₈ and allow us to determine the torsional splittings in the υ₃ + 2υ₄ state. The vibration-rotation constants of υ₄ + υ₆, υ₄ + υ₈ and υ₃ + 2υ₄, several interaction parameters and the torsional splitting of υ₃ + 2υ₄ have been determined by least-squares fit of 1391 observed transition wavenumbers, with an overall standard deviation σ = 0·75 × 10^?3 cm^?1. The vibrational wavenumbers found for the four torsional components of (υ₃ + 2υ₄)? υ₄ are υ(E_3d) = 1040·961 82(809)cm^?1, υ(A_3d) = 1041·218 27(865)cm^?1, υ(E_3s) = 1041·225 23(662)cm^?1 and υ(A_1s) = 1041·407 77(633)cm^?1. These are anomalous for both the order of the torsional components and the magnitudes of their separations. We believe that this is mainly due to the interactions of υ₃ + 2υ₄ with the torsional manifolds with υ₃ = 0 and υ₃ = 2, through the vibration-torsion Hamiltonian term (?V ₆/?q ₃)q ₃cos (6γ)]/2. The further observation of a few doublets of υ₈ and υ₃ + υ₄ at resonance provides information on the torsional splitting of the latter state.     

Volume properties and compressibility of the graphite-potassium-mercury compounds

Abstract

The volume properties of graphite intercalation compounds (GIGS) C4KHg and of the initial intermetallic compounds KHg and KHg₂ have been investigated in the piston-cylinder apparatus, using the direct volumetric technique, under pressures up to 25 kbar. The compounds, average compressibility K₊, was determined to be 3.8×10^?3 kbar^?1 for C₄KHg, 3.0×10^?3 kbar-^?1 for C₈KHg, 4.8×10^?1 kbar^?1 for KHg, and 4.0 ×10^?1 kbar^?1 for KHg₂ at pressures of 0-20 kbar. The compressibility of the “two-dimensional” KHg layer in the GIC under various pressure conditions has been estimated. These estimates permit comparison of KHg properties in the “three dimensional” and “quasi-two dimensional” states. It was concluded that the influence of the graphite matrix on the intercalant is insignificant for this type ternary GIC.     

Energy Shift of the 4f 136s 1 Excited States of Yb2+ from Gas Phase to the CsCaBr3 Solid

ABSTRACT

Ab initio calculations on Yb²⁺-doped CsCaBr₃ show a large increase (20000 cm^?1) of the 4f ¹⁴ → 4f ¹³6s ¹ transitions from gas phase to CsCaBr₃, due to large embedding effects originated beyond the first bromide coordination shell. The 4f ¹³6s ¹ states of (YbBr₆)^4- in vacuo undergo a sudden energy and electron density change at short Br-Yb distances resulting in the formation of an Yb-trapped exciton, which evolves to full ionization, making Yb(II) unstable in hexabromide coordination in gas phase. Embedding in CsCaBr₃ localizes the 6s electron inside the Br₆ cage, which increases the 6s-Br₆ repulsion and increases the energy of the 4f ¹³6s ¹ states.     

Optical properties and radiation effects in layered crystals of (CnH2n+nNH3)2MCl4: n = 1, 2, 3; M = Cd,Cu, Mn

Abstract

A new absorption band has been found at 5.10 eV in (C _n H_{2n + 1}NH₃)₂CdCl₄: n = 1, 2, 3 in addition to the absorption bands of CdCl₂ whose electronic structure resembles the former crystals. The energy of the additional peak shifts with temperature by as much as 0.38 eV from 5.10eV at room temperature (RT) to 5.48 eV at liquid nitrogen temperature. This large peak shift is attributed to a structural phase transition between these two temperatures. A new type of electron center has been found in these crystals (M = Cd, Mn; n = 1, 2, 3) irradiated with X-rays at 15 K in addition to the Cl₂ ^?. This shows optical absorption bands (IR bands) in the infrared region of 10 ～ 20 kcm ^?1. The IR bands are assigned to an electron center where an electron is trapped at an ammonium site in the neighborhood of a Cl^? vacancy.