The heat capacity of the layer compounds (CH3CH2CH2NH3)2MnCl4 and (CH3CH2CH2NH3)2CdCl4 from 10 K TO 300 K

The heat capacity of the layer compounds tetrachlorobis (n-propylammonium) manganese II and tetrachlorobis (n-propylammonium) cadmium II, (CH₃CH₂CH₂NH₃)₂MnCl₄ and (CH₃CH₂CH₂NH₃)₂CdCl₄ respectively, has been measured over the temperature range 10 K ?T ? 300 K.Two known structural phase transitions were observed for the Mn compound in this temperature region: at T = 112.8 ± 0.1 K (ΔH_t= 586 ± 2 J mol^?1; ΔS_t = 5.47 ± 0.02 J K^?1mol^?1) and at T =164.3 ± (ΔH_t = 496 ± 7 J mol^?1; ΔS_t =3.29 ± 0.05 J K^?1mol^?1). The lower transition is known to be from a monoclinic structure to a tetragonal structure, while the upper is from the tetragonal phase to an orthorhombic one. From comparison with the results for the corresponding methyl Mn compound it is deduced that the lower transition primarily involves changes in H-bonding while the upper transition involves motion in the propyl chain.A new structural phase transition was observed in the Cd compound at T= 105.5 ± 0.1 K (ΔH_t= 1472.3 ± 0.1 J mol^?1; ΔS_t = 13.956 ± 0.001 J K^?1mol^?1), in addition to two transitions that have been observed previously by other techniques. The higher of these transitions(T = 178.7 ± 0.3 K; ΔH_t = 982 ± 4 J mol^?1 ΔS_t = 6.16 ± 0.02 J K^? mol^?1) is known to be between two orthorhombic structures, while the structural changes at the lower transition (T= 156.8 ± 0.2 K; ΔH_t = 598 ± 5 J mol^?1, ΔS_t = 3.85 ± 0.03 J K^?1 mol^?1) and at the new transition are not known. It is proposed that these two transitions correspond respectively to the tetragonal to orthorhombic and monoclinic to tetragonal transitions in the propyl Mn compounds.In addition to the structural phase transitions (CH₃CH₂CH₂NH₃)₂MnCl₄ magnetically orders at t? 130 K. The magnetic contribution to the heat capacity is deduced from the heat capacity of the corresponding diamagnetic Cd compound and is of the form expected for a quasi 2-dimensional Heisenberg antiferromagnet.     

Non-cubic Mn2+-centers in BaF2

The EPR spectra of thermally treated BaF₂: Mn samples is reported. After thermal annealing at 900 K a trigonal Mn²⁺ center with g=2.000±0.005, |D|=2725±40MHz, |A|=265±10MHz, $\text{D}\text{A}\text{>0}$, is observed. Annealing at 1200 K produces an orthorhombic Mn²⁺ center with g=2.00±0.01, |D|=2430±40MHz, |E|=570±20MHz, |A|=265±10MHz, $\text{D}\text{A}\text{<0}$. The superhyperfine (SHF) structures due to interactions with the neighbouring fluorines indicates that the trigonal manganese interacts with four fluorines, three of them equivalent. The orthorhombic Mn²⁺ shows interaction with four equivalent fluorine nuclei.     

The heat capacity of the layer compound tetrachlorobis (methylammonium) manganese—II (CH3NH3)2MnCl4, from 10 to 300k

The heat capacity of the layer compound, tetrachlorobis (methylammonium) manganese II, (CH₃NH₃)₂MnCl₄, has been measured over the range 10K <T<300K. In this region, two structural phase transitions have been observed previously by other techniques: one transition is from a monoclinic low temperature (MLT) phase to a tetragonal low temperature (TLT) phase, and the other is from TLT to an orthorhombic room temperature (ORT) phase. The present experiments have shown that the lower transition (MLT→TLT) occurs at T = 94.37±0.05K with ΔH_t = 727±5 J mol^?1 and ΔS_t = 7.76±0.05 J K^?1 mol^?1, and the upper transition (TLT→ORT) takes place at T = 257.02±0.07K with ΔH_t = 116±1J mol^?1 and ΔS_t = 0.451±0.004 J K^?1mol^?1. These results are discussed in the light of recent measurements on (CH₃NH₃)₂CdCl₄, and also with regard to a recent theoretical model of the structural phase transitions in compounds of this type.In addition to the structural phase transitions, (CH₃NH₃)₂MnCl₄ also undergoes magnetic ordering at T < 150K. The magnetic component to the heat capacity, as deduced from a corresponding states comparison of the heat capacity of the present compound with that of the Cd compound, is shown to be consistent with the behaviour expected for a quasi 2-dimensional Heisenberg antiferromagnet.     

Phonon coupled cooperative low-spin 1A1high-spin 5T2 transition in [Fe(phen)2(NCS)2] and [Fe(phen)2(NCSe)2] crystals

Heat capacities of [Fe(phen)₂(NCS)₂] and [Fe(phen)₂(NCSe)₂] were measured between 13⁵ and 375 K. A heat capacity anomaly due to the spin-transition from low-spin ¹A₁ to high-spin π₂ electronic ground state was found at 176·29 K for the SCN-compound and at 231·26 K for the SeCN-compound, respectively. Enthalpy and entropy of transition were determined to be ΔH = 8·60 ± 0·14 kJ mol^?1 and ΔS = 48·78 ± 0·71 J K^?1 mol^?1 for the SCN-compound and ΔH = 11·60 ± 0·44 kJ mol^?1 and ΔS = 51·22 ± 2·33 J K^?1 mol^?1 for the SeCN-compound. To account for much larger value of ΔS compared with the magnetic contribution, we suggest that there is significant coupling between electronic state and phonon system. We also present a phenomenological theory based on heterophase fluctuation. Gross aspects of magnetic, spectroscopic, and thermal behaviors were satisfactorily accounted for by this model. To examine closely the transition process, infrared spectra were recorded as a function of temperature in the range 4000 ? 30 cm^?1. The spectra revealed clearly the coexistence of the ¹A₁, and the ⁵T₂ ground states around T_c.     

Measurement of the branching ratios for Kμ2+, Kπ2+, Ke3+ and Ke3+ decays using a magnetic spectrometer with streamer chambers

The momenta of ～30 000 charged particles from K⁺ decays were measured using a magnetic spectrometer with streamer chambers. The ratio R = Γ(K_π2⁺)/Γ(K_μ2⁺) = 0.3355 ± 0.0057 was obtained. Our values for the branching ratios are: (63.18±0.43)% for K_μ2⁺, (21.18±0.33)% for K_π2⁺, (3.33±0.51)% for K_μ3⁺, (4.99±0.54)% for K_e3⁺.     

ESR study of Fe3+ and Mn2+ ions on trigonal sites in ilmenite structure MgTiO3

Electron spin resonance has been observed for Fe³⁺ and Mn²⁺ ions occupying sites with trigonal symmetry in undoped and doped Verneuil-grown crystals of the ilmenite type compound MgTiO₃. At 300 K, the fine structure parameters in the spin Hamiltonian are (in 10^?4cm^?1) D = +844 (± 1), (a? F) = +118 (± 1), a = 69 (± 7) for Fe³⁺ and D = +164 (± 1), (a ? F) = +10.2 (± l), a = 7.0 (± 1) for Mn²⁺. These values are compared with literature data for Fe³⁺ and Mn²⁺ in other oxides, especially Al₂o₃, with particular reference to the recent “superposition” theory of the effect of a trigonal distortion. From the orientation of the axes of cubic pseudosymmetry of the spin Hamiltonian, and with the assumption that a has the same sign for both ions, it is proposed that Fe³⁺ and Mn²⁺ occupy the same octahedral site, namely the Mg²⁺ site. Anomalous line splittings observed for one sample were attributed to twinning on (0001) or {1120} planes.     

Tunable laser study of the ν10 + ν11 band of cyclopropane

Diode laser measurements of the ν₁₀ + ν₁₁ (l_tot = ±2) perpendicular band of cyclopropane have led to the assignments of roughly 600 lines in the 1880–1920-cm^?1 region. Most of the spectra were recorded and stored in digital form using a rapid-scan mode of operating the laser. These spectra were calibrated, with the aid of a computer, by reference to the R lines of the ν₁ + ν₂ band of N₂O. The ground state constants we obtained are (in cm^?1) B = 0.670240 ± 2.4 × 10^?5, D_J = (1.090 ± 0.054) × 10^?6, D_JK = (?1.29 ± 0.19) × 10^?6, D_K = (0.2 ± 1.1) × 10^?6. The excited state levels are perturbed at large J values, presumably by Coriolis couplings between the active E′(l_tot = ±2) and the inactive A′(l_tot = 0) states. Effective values for the excited state constants were obtained by considering only the J < 15 levels. The A₁-A₂ splittings in the K′ = 1 excited states were observed to vary as q_effJ(J + 1), with q_eff = (2.17 ± 0.17) × 10^?4 cm^?1.     

Vibrational spectra and force constants of symmetric tops: Rovibrational analysis of 2ν6 and 2ν6 − ν6 of H3Si35Cl and H3Si37Cl,and a new method for the determination of A0 and DK0

The gas-phase ir spectra of monoisotopic H₃Si³⁵Cl [35] and H₃Si³⁷Cl [37] in the 2ν₆ region near 1300 cm^?1 have been studied with a resolution of 0.05 cm^?1. A total of 467 and 1206 lines have been assigned for [35] and [37], respectively, and analyzed by a least-squares procedure, σ(J, K) ～ 6 × 10^?3cm^?1, to yield three parameters for the 2ν₆⁰ and six for the 2ν₆^±2 states for both isotopomers. In the ν₆ region $\text{32}\text{47}$ and $\text{127}\text{150}$ lines have been assigned to the hot bands 2ν₆⁰ ? ν₆^±1 and 2ν₆^±2 ? ν₆^±1 of [35] and [37], respectively. While a hot band 2ν_t⁰ ? ν_t^±1 does not provide any information above that available from ν_t^±1 and 2ν_t⁰, a hot band 2ν_t^±2 ? ν_t^±1 may supply extra data concerning the ground state. A new method for the evaluation of A₀ and D_K⁰ from combination differences of ν_t^±1, 2ν_t^±2, and 2ν_t^±2 ? ν_t^±1 of a symmetric top with C_3v symmetry is presented. Application to [35] and [37] yielded A₀ of 2.8447(5) and 2.8437(3) cm^?1, and D_K⁰ of 2.12(20) and 2.38(9) × 10^?5 cm^?1, respectively.     

Electron paramagnetic resonance of Gd3 in YCl3·6H2O

The electron paramagnetic resonance spectrum of Gd³⁺ in YCl₃·6H₂0 with $\text{1}\text{100}$ dilution of Gd/Y ions, has been studied with an X-band spectrometer at 295, 77 and 1.77°K and with a K-band spectrometer at 295 and 77°K. The individual values of all the parameters are evaluated from the data at the three temperatures. In particular, the following values for the g-tensor and the zero-field splitting parameters b₂⁰ and b₂² are obtained from X-band data: at 295°K, g_zz = 1.994±0.005, g_xx = 1.992±0.005, g_yy = 1.997±0.005, b₂⁰ = 1.898 ±0.015 GHz, b₂² = ?2.247 ± 0.015GHz; at 77°K, g_zz = 1.999±0.008, g_xx = 2.000±0.008, b₂⁰= 1.978 ±0.022 GHz, b₂² = ?1.574±0.022GHz; at 1.77°K, g_zz = 2.002±0.010, g_xx = 1.990 ±0.010, b₂⁰ = 2.011 ± 0.025 GHz, b₂² = ?1.650 ±0.025 GHz. (The K-band values are found to be consistent with the X-band values). From the angular dependence of the data in the ZX plane (i) the angle X₀ which the Z axis makes with the a vector of the unit cell, is determined to be 58.00 ±0.25° and (ii) the existence of pseudo-symmetry axes at ±5° from the Z axis in the ZX plane as found by heat capacity and specific heat data has been confirmed. An estimate is also made of the extent of admixture of the excited ${}^6\text{P}{}_{\mathrm{<mtext>7</mtext><mtext>2</mtext>}}$ state with the ground state ${}^8\text{S}{}_{\mathrm{<mtext>7</mtext><mtext>2</mtext>}}$.     

The ν2 and ν4 bands of AsH3

The infrared absorption of arsine, AsH₃, between 750 and 1200 cm^?1 has been recorded at a resolution of 0.006 cm^?1. Altogether 2419 transitions, including nearly 700 “perturbation allowed” transitions with Δ∥k ? l∥ = ±3, ±6, and ±9, have been assigned to the ν₂(A₁) and ν₄(E) bands. Splitting of the transitions for K″ = 3, 6, and 9 was also observed. To fit the rotational pattern of the v₂ = 1 and v₄ = 1 vibrational states up to J = 21, all the experimental data were analyzed simultaneously on the basis of a rovibrational Hamiltonian which took into account the Coriolis interaction between ν₂ and ν₄ and also included several essential resonances within them. The derived set of 38 significant spectroscopic parameters reproduced the 2328 transition wavenumbers retained in the final fit within the accuracy of the experimental measurements.     

Magnon Raman scattering in CoBr2

The one-magnon Raman spectrum of CoBr₂ has been investigated as a function of temperature, and peak frequency, integrated intensity and width parameters obtained. The results obtained for the band energy at low temperature (22.2 ± 0.2 cm^-1 at 5.7.K) are in good agreement with AFMR and neutron scattering results. The one-magnon energy renormalises relatively slowly with increasing temperature and is about 15 cm^-1 at T_N = 19 K, whereas the integrated intensity approaches zero like the magnetization at T_N and the width diverges. A low intensity band at 26.8 ± 1 cm^-1 (7.6K) may be due to two-magnon scattering from spin waves along the c-axis.     

The heat capacity of LaPd3 and PrPd3 at low temperature

Values of γ=0.33±0.01 mJ/K²·g atom and θ_D=176±1 K were found for LaPd₃. PrPd₃ shows magnetic ordering below 0.6 K and a Schottky anomaly whose maximum lies around 1.8 K. The crystalline field at the Pr³⁺ site creates a Γ₃ (doublet) excited state lying 4 K above the Γ₅ (triplet) ground state.     

Dielectric and AC ionic conductivity investigations in K3H(SeO4)2 single crystal

Optical observation under the polarizing microscope and DSC measurements on K₃H(SeO₄)₂ single crystal have been carried out in the temperature range 25-200 °C. It reveals a high-temperature structural phase transition at around 110 °C. The crystal system transformed from monoclinic to trigonal. Electrical impedance measurements of K₃H(SeO₄)₂ were performed as a function of both temperature and frequency. The electrical conduction and dielectric relaxation have been studied. The temperature dependence of electrical conductivity indicates that the sample crystal became a fast ionic conductor in the high-temperature phase. The frequency dependence of conductivity follows the Jonscher's universal dynamic law with the relation σ(ω)=σ(0)+Aωⁿ, where ω is the frequency of the AC field, and n is the exponent. The obtained n values decrease from 1.2 to 0.1 from the room temperature phase to fast ionic phase. The high ionic conductivity in the high-temperature phase is explained by the dynamical disordering of protons between the neighboring SeO₄ groups, which provide more vacant sites in the crystal.     

The absorption spectrum of CO2 around 7740 cm-1

Absolute intensities of the vibration-rotation lines of the CO₂ 401_II←000 band 7734 cm^-1 are measured under high-resolution, low-pressure conditions by use of a White-type 25-m base-path, absorption cell together with a 5-m Czerny-Turner spectrometer. The total band intensity S_B, the purely vibrational transition moment

, and the vibration-rotation interaction constant ζ are calculated from the intensity measurements. The values obtained for these parameters are S_B(401_II) = (7.06±0.07) × 10^-5 cm^-2 atm^-1_293°K,

= (3.08±0.03)×10^-5 debye, and ζ = (2.5±0.5)×10^-4. The intensity of the associated “hot band” 411_II←010 is also determined and found to be S_B(411_II←010) = (0.53±0.02)×10^-5 cm^-2 atm^-1_293°K.     

EPR spectra of colour centres in x-irradiated BaCl2:K+ and BaCl2:Ag+

X-irradiation at 80°K leads to the formation of V_K centres and, in addition, perturbed F centres in the case of BaCl₂:K⁺. The V_K centres spectra exhibit a superhyperfine structure. A warming to 130°K of crystals X-irradiated at 80°K causes the V_K centres to be perturbed, and besides leads to the formation of (AgCl₄)^2? complexes in BaCl₂:Ag⁺.     

Pion-pion phase shift and K2π decay

We remark that, using the Cabibbo transformation properties for the weak Hamiltonian we can obtain Δ₀ = δ₀⁽⁰⁾ (s = M_K⁽²⁾ (s = M_K²) from the experimental decay rates for K_s → 2π, K⁺ → π⁰π⁺, obtaining δ₀ = 58.0° ± 4.6°. This result implies in particular a value of ≈ 0.6 for the S-wave isospin zero scattering length, in accordance with K_e4 results but in violent disagreement with Weinberg's calculation.     

Low temperature ESR of K2Pt(CN)4Br0.3. 3.2 H2O

Electron spin resonance has been observed in high purity single crystals of K₂Pt(CN)₄Br_0.3·3.2H₂O, (KCP), in the temperature range of 4.22–80 K. Two types of paramagnetic species are found to dominate the spectrum. One of these is an inhomogeneously broadened line showing no resolved hyperfine splitting and having g_∥ = 1.946 ± 0.003 and g⊥ = 2.340 ± 0.003. The second paramagnet is identified as a Cu²⁺ impurity center with g_∥ = 2.231 ± 0.003, g⊥ = 2.079 ± 0.002 and hyperfine tensor A_∥ = 467 MHz, A_⊥ = 70 MHz.     

EPR of V2+ in SrCl2

The X-band EPR spectrum of SrCl₂:V has been measured at liquid nitrogen temperature. A signal associated with V²⁺ in a site of trigonal symmetry is observed. The EPR data have been explained using the spin hamiltonian $\textcolor{red}{}\text{= μ}{}_{\mathrm{\beta }}\text{H}\text{g}\text{?}\text{S}\text{+ D[S}{}^2{}_{\mathrm{z}}\text{?}\text{1}\text{3}\text{S(SH)] +}\text{S}\text{A}\text{?}\text{I}$, with D ? hv, g_∥ = 1.957 ± 0.004, g₆ = 1.954 ± 0.004, A_∥ = 230 ± 5 MHz, A₆ = 235 ± 5 MHz. This V²⁺ defect is similar to those previously reported in fluoride crystals with the fluorite structure.     

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.     

A study of the decay KL0 → π±e∓νe

In a study of charged K_L⁰ three-body decays a sample of 6668 K_L⁰ → π^±e^?ν candidates has been obtained. The Dalitz plot distribution is in agreement with V ? A theory, and limits are presented for scalar and tensot contributions to the weak current. Using a conventional expansion for the form factor f₊ we find λ₊ = 0.055 ± 0.010 with systematic effects estimated at ± 0.01.