Dynamics of BF 4 - anion reorientation in the spin-crossover compound [Fe(1-n-propyl-1H-tetrazole) 6 ](BF 4 ) 2 and in its Zn II analogue

¹⁹ F and ¹¹ B spin-lattice relaxation times were measured in [ Zn ( ptz ) ₆ ] ( BF ₄ ) ₂ and in the spin-crossover compound [ Fe ( ptz ) ₆ ] ( BF ₄ ) ₂ . For both compounds BF ₄ ^- anion reorientation is active above 50 K. For [ Zn ( ptz ) ₆ ] ( BF ₄ ) ₂ , the anion-reorientation dynamics is different in the temperature regions of 50-90 K, 90-120 K, and above 150 K; between 120 and 150 K it changes rapidly reflecting a structural change. In [ Fe ( ptz ) ₆ ] ( BF ₄ ) ₂ the mechanism for the paramagnetic relaxation involving the ¹⁹ F nuclei is found to be of the diffusion-limited type according to the theory of Lowe and Tse. The present results prove that the spin-crossover takes place in a dynamic surrounding and not in a static crystal lattice. Received 09 February 1999 and Received in final form 14 June 1999     

Interpretation of the Vapor Pressure Isotope Effect of BF3

The available experimental data on the vapor pressure isotope effect (VPIE) of BF₃ are interpreted within the framework of the statistical theory of isotope effects in condensed systems. It is shown that the temperature dependence of the VPIE of ¹⁰BF₃/¹¹BF₃ observed by Rayleigh distillation experiments cannot be rationalized at all, while the curie obtained by vapor pressure difference measurements seems to be too steep below the boiling point.     

High-resolution infrared and microwave study of 10BF2 OH and 11BF2OH: the 5, 6l, 71, 8l, 91 and 81 91 vibrationally excited states

Abstract

High-resolution (≤2.4×10^?3cm^?1) Fourier transform infrared spectra of gas-phase ¹⁰B-enriched isotopic and natural samples of BF₂OH (difluoroboric acid) were recorded in the 400–4000 cm^?1 spectral range. Starting from the results of a previous study [Collet, D., Perrin, A., Burger, H., and Flaud, J.-M., 2002, J. Molec. Spectrosc. 212, 118], which involved the v ₈ ¹⁰BF₂ out-of-plane bending) and v₉ (OH torsion) bands of ¹¹BF₂OH, it has been possible to perform the first rovibrational analysis of the v ₅ ¹⁰BF₂ bending), v ₈ , v ₉ and v ₈+v ₉ bands of’¹¹BF₂OH, and of the v ₇ (F₂BO in-plane bending), v ₅, and v ₈+v₉ bands of ¹¹BF₂OH up to very high rotational quantum numbers. In addition, microwave transitions within the 5¹, 6¹, 7¹ and 8¹ vibrational states of ¹¹BF₂OH were measured using predictions from ab initio calculations [Breidung, J., Demaison, J., D'Eu, J.-F., Margules, L., Collet, D., Mkadmi, E. B., Perrtn, A., And Thiel, W., 2004, J. Mol. S ectrosc. (in press)]. The v ₅, v ₈, v ₉ and v ₈+v ₉ bands of’ bands of ¹⁰BF₂OH and the v ₈+v ₉ band of'BF₂OH are not significantly affected by ptrturbations, and the experimental 5¹, 8¹ and 9¹ of ¹⁰BF₂OH and the 8¹9¹ energy levels of BF20H and ¹⁰BF₂OH could be reproduced using a simple Watson-type Hamiltonian. For the v ₅ and v ₇ bands of ¹¹BF₂OH, C-type Coriolis interactions coupling the 5¹ and 7¹ energy levels with those of the 7² and 6¹ dark states, respectively, were accounted for in the calculation. In addition, an updated set of rotational parameters was provided for the unperturbed 8¹ and 9¹ vibrational states of ¹¹BF₂OH using the data from our previous analysis. In all these cases, the upper state parameters derived in this work enabled the reproduction of both the infrared and microwave data to within experimental uncertainties.     

Low temperature differential magnetization of Ni(ClO4)26NH3 and Ni(BF4)26NH3

The differential magnetization of Ni(ClO₄)₂6NH₃ and Ni(BF₄)₂6NH₃ was measured as a function of temperature (20 to 0.3 K) and magnetic field (up to 40kOe). An antiferromagnetic transition was found at T_N = 0.45 K for the Ni(ClO₄)₂6NH₃ and T_N = 0.43 K for the Ni(BF₄)₂6NH₃, and a portion of the magnetic phase diagram was determined. The interpretation of the data in terms of a uniaxial model yielded (D/k) ～ 0.2 K for both salts.     

Theory of electronic structure and nuclear quadrupole interactions in the BF3–NH3 complex and methyl derivatives

Magnetic Hyperfine and Nuclear Quadrupole Interactions (HFI and NQI) are now important tools for characterization of systems of interest in materials research and industry. Boron-Trifluoride is an inorganic compound that is very important in this respect as a catalyst in chemical physics research and industry, forming complexes in the process with compounds like ammonia, water and methyl alcohol. The present paper deals with the BF₃–NH₃ complex and methyl derivatives BF₃NH_x(CH₃)_3?x for which we have studied the electronic structures, binding energies, and ¹⁹F* (I?=?5/2) nuclear quadrupole interactions using the first-principles Hartree–Fock–Roothaan procedure combined with electron correlation effects. Our results for the ¹⁹F* nuclear quadrupole coupling constant (e ² qQ/h) in units of MHz compare well with experiment. Trends in the binding energies and NQI parameters between the complexes are discussed.     

Electrochemical properties of Li[CnF2n+1BF3] as electrolyte salts for lithium-ion cells

The fundamental electrochemical properties of lithium perfluoroalkyltrifluoroborates Li[C_nF_2n+1BF₃] (n = 1∼4) were evaluated as electrolyte salts for lithium-ion battery in comparison with LiBF₄ and LiPF₆. Li[C_nF_2n+1BF₃] showed higher electrolytic conductivities than LiBF₄ in aprotic solvents. In these series, the conductivities decreased with the perfluoroalkyl group being longer, and Li[C₂F₅BF₃] exhibited a comparable conductivity to LiPF₆. The relationship between the conductivity and the anion size showed that the anion with a moderate size is in favor of obtaining high conductivities. The limiting oxidation potentials determined by linear sweep voltammetry demonstrated that Li[C_nF_2n+1BF₃] were less resistant against oxidation than LiBF₄. The HOMO energies and ionization energies of [C_nF_2n+1BF₃]⁻ calculated by ab initio molecular orbital (MO) theory and density functional theory (DFT) supported this observation, however, there was no accuracy to explain the effect of the chain length of perfluoroalkyl groups on the limiting oxidation potentials. The cell performances of a LiC₆/Li_0.5CoO₂ cell using Li[C₂F₅BF₃] were comparable to those using LiPF₆ at room temperature, however, it deteriorated at elevated temperature due to the reaction on the cathode.     

An ESR study of phase transitions in crystals of M(BF4)2·6H2O (M = Fe,Co, Ni,Zn)

From a temperature dependent ESR study of Mn²⁺-doped crystals of M(BF₄)₂·6H₂O, M Zn, Co and Ni, new structural phase transitions have been detected and studied. First order structural phase transitions occur in Co(BF₄)₂·6H₂O at T₁ ~ 281K, T₂~189 K and T₃~172K (during cooling), in Zn(BF₄)₂·6H₂O at T₁ ~ 286 K and in Ni(BF₄)₂·6H₂O at T₁ ~ 301 K. A continuous phase transition occurs in Co(BF₄)₂·6H₂O at T_p ~ 257 K, in Zn(BF₄)₂·6H₂O at T_p ~ 277 K and in Ni(BF₄)₂·6H₂O at T_p ~ 294 K. The ESR spectral characteristics suggest similarities in the structures of these fluoroborate compounds in the phase above T₁ with the room temperature structure of Mg(ClO₄)₂·6H₂O. All these compounds are found to have a tendency to crystallise in a triply-twinned pseudo-hexagonal form, although the unit cell above T₁ is found to be orthorhombic. The structural changes related to the water octahedron around the metal at T₁ were found to be very small and basically the same for these three compounds. Although the unit cell structure of Fe(BF₄)₂·6H₂O above the first order phase transition temperature T₁ was found to be similar to that of the other fluoroborate compounds, the structural changes occurring at T₁ appeared to be quite different. The low temperature thermal behaviour differs considerably in the Co, Fe and Zn compounds.     

Coherent Raman spectra of the ν1 mode of BF3 and BF3

High resolution (0.001 cm⁻¹) coherent anti-Stokes Raman spectroscopy (CARS) was used to directly examine the ν₁ symmetric stretching mode of the planar symmetric D_3h molecules ¹⁰BF₃ and ¹¹BF₃. Simulations of the spectra were done using ν₁ rovibrational parameters deduced from published infrared hot-band and difference-band studies and the close similarity to the observed CARS spectra confirms the validity of the infrared constants. No significant perturbations by Fermi resonance or Coriolis interactions with nearby states are observed, in marked contrast to the case of sulfur trioxide, a similar D_3h molecule recently studied. In the harmonic approximation, the ¹⁰BF₃ and ¹¹BF₃ν₁ Q-branches would be identical since the isotopic substitution is at the center of mass but, interestingly, the ν₁ stretching frequency for ¹¹BF₃ is found to be 0.198 cm⁻¹higher than for the lighter ¹⁰BF₃ isotopomer. This counterintuitive result is reproduced almost exactly (0.200 cm⁻¹) by ab initio calculations (B3LYP/cc-pVTZ) that included evaluation of cubic and quartic force constants and x_ij anharmonicity constants. The ab initio computations also predict to within 1% the ΔB, ΔC changes in the rotational constants in going from the ground state to the v₁ = 1 vibrational level. The results illustrate nicely the complementary interplay of modern infrared, Raman, and ab initio methods in obtaining and analyzing rovibrational spectra.     

The analysis of symmetric rotor Raman spectra: The pure rotational spectrum of 11BF3

The pure rotational Raman spectrum of ¹¹BF₃ has been photographed. Great care was taken in the analysis to consider all the unresolved components under each observed Raman line profile. If this is ignored, systematic errors result. The final set of molecular constants obtained was B₀ = 0.34502(±3 × 10^?5)cm^?1, D_J = 4.38(±0.10) × 10^?7cm^?1, and D_JK = ?9.1(±1.0) × 10^?7cm^?1.     

Fe2+ spin transition in [Fe(trz)(Htrz)2](BF4) as evidenced by a variable temperature EPR study

The EPR of Fe³⁺ ions has been used for the first time to evidence a low-spin (S=0) to high-spin (S=2) transition of Fe²⁺ ions in an octahedral ferrous complex [Fe(trz)(Htrz)₂](BF₄). The temperature dependence of the intensity of the Fe³⁺ EPR line atg=4.3 reveals a spin transition which occurs for the Fe²⁺ ions, with hysteresis. The transition temperatures areT _c↑=374 K in the warming mode andT _c↓=345 K in the cooling mode. The analysis of the EPR spectral data indicates the presence of a structural phase transition accompanying the spin transition.     

An EPR investigation of the phase transitions and cooperative ordering phenomena of pentaamminecopper(II) polyhedra in Cu(NH3)5X2 [X=BF4, CIO4; Br]

The results of powder and single-crystal EPR studies on Cu(NH₃)₅X₂ compounds [X=BF₄, CIO₄; Br] give evidence that phase transitions from a cubic α-phase (g _i ?2.12) with an anti-K₂PtCl₆ type structure to low-temperature β-phases with reduced symmetry occur, which are induced by ordering processes of the vacancies □ of elongated [Cu(NH₃)₅□]²⁺ pseudo-octahedra. The type of order is crucially controlled, by the nature of the anion. In the case of the BF ₄ ^? and ClO ₄ ^? salts the large anions are structure-determining leading to a slightly disturbed antiferrodistortive order of the elongated Cu^IIN₅ square pyramids atT _c?155 K and <130 K, respectively. The resulting pseudo-tetragonal β-structure of the BF ₄ ^? compound is characterized by two rhombic crystalg tensors (g ₂ ^B∥g ₁ ^A=2.173;g ₁ ^B∥g ₂ ^A=2.124;g ₃ ^B∥g ₃ ^A=2.071). The dibromide salt undergoes a first-order phase transition atT _c=285 K from cubic to tetragonal with a rather lowc/a ratio of about 0.9. The Cu^IIN₅ square pyramids in the low-temperature β-structure are arranged in this case according to a “mixed ferrodistortive/antiferrodistortive” order pattern. Interestingly enough the angular dependence of theg tensor components indicate further structural changes with decreasing temperature, which are of rather local character, however, not correlated with a second phase transition. Atomic displacements lead to reduced Cu^II?Cu^II distances within certain antiferrodistortive pairs, as evidenced by EPR spectroscopy. The molecularg-values at higher temperatures (g _∥=2.243;g _⊥=2.056) transform to those of pairs with canting angles of about 80° (g ₁=2.168;g ₂=2.138;g ₃=2.046).     

Phase transitions and molecular motions in [Zn(NH3)4](BF4)2 studied by nuclear magnetic resonance, infrared and Raman spectroscopy

Middle infrared absorption, Raman scattering and proton magnetic resonance relaxation measurements were performed for [Zn(NH₃)₄](BF₄) in order to establish relationship between the observed phase transitions and reorientational motions of the NH₃ ligands and BF₄⁻ anions. The temperature dependence of spin-lattice relaxation time (T₁(¹H)) and of the full width at half maximum (FWHM) of the bands connected with ρ_r(NH₃), ν₂(BF₄) and ν₄(BF₄) modes in the infrared and in the Raman spectra have shown that in the high temperature phase of [Zn(NH₃)₄](BF₄)₂ all molecular groups perform the following stochastic reorientational motions: fast (τ_R≈10⁻¹² s) 120° flips of NH₃ ligands about three-fold axis, fast isotropic reorientation of BF₄⁻ anions and slow (τ_R≈10⁻⁴ s) isotropic reorientation (“tumbling”) of the whole [Zn(NH₃)₄]²⁺ cation. Mean values of the activation energies for uniaxial reorientation of NH₃ and isotropic reorientation of BF₄⁻ at phases I and II are ca. 3 kJ mol⁻¹ and ca. 5 kJ mol⁻¹, respectively. At phases III and IV the activation energies values for uniaxial reorientation of both NH₃ and of BF₄⁻ equal to ca. 7 kJ mol⁻¹. Nearly the same values of the activation energies, as well as of the reorientational correlation times, at phases III and IV well explain existence of the coupling between reorientational motions of NH₃ and BF₄⁻. Splitting some of the infrared bands at T_C2=117 K suggests reducing of crystal symmetry at this phase transition. Sudden narrowing of the bands connected with ν₂(BF₄), ν₄(BF₄) and ρ_r(NH₃) modes at T_C3=101 K implies slowing down (τ_R?10⁻¹⁰ s) of the fast uniaxial reorientational motions of the BF₄⁻ anions and NH₃ ligands at this phase transition.     

Quadrupole relaxation enhancement and polarisation transfer in DMSO solution of [Bi(NO3)3(H2O)3]*18-crown-6 in solid state

ABSTRACT

¹H spin-lattice relaxation studies have been performed for pure [Bi(NO₃)₃(H₂O)₃]*18-crown-6 in powder and its solution in dimethyl sulfoxide (DMSO). The experiments have been carried out in the frequency range of 10?kHz–30?MHz and the temperature range of 240–277?K; at 277?K the solution is already frozen. The ¹H relaxation of pure [Bi(NO₃)₃(H₂O)₃]*18-crown-6 has been interpreted in terms of three dynamical processes. Quadrupole Relaxation Enhancement effects have been observed in the frozen DMSO solution of [Bi(NO₃)₃(H₂O)₃]*18-crown-6. The specific mechanisms of the ¹H spin-lattice relaxation enhancement have been discussed distinguishing between effects caused by time independent (residual) and fluctuating ¹H-²⁰⁹Bi dipole-dipole interactions.     

Structural and energetic properties of alkylfluoride–BF3 complexes in the gas phase and condensed‐phase media: computations and matrix infrared spectroscopy

We have undertaken an experimental and computational study of the structural properties of a few alkylfluoride–BF₃ complexes (RF′–BF₃), which are proposed intermediates in a certain class of Friedel–Crafts reactions. Using density functional theory and second‐order Møller–Plesset calculations, we have obtained gas‐phase structures, frequencies, and B–F′ bond potentials for CH₃F–BF₃, (CH₃)₂CHF–BF₃, and (CH₃)₃CF–BF₃. All the complexes are weakly‐bonded in the gas phase, with B–F′ distances (X3LYP/aug‐cc‐pVTZ) of about 2.4 Å and binding energies (MP2/aug‐cc‐pVTZ) ranging from 5.4 and 6.7 kcal/mol. Accordingly, gas‐phase bond potentials are relatively shallow and flat for these complexes. However, even though the inner walls of the potentials are rather soft (the energies rise by only about 5 to 10 kcal/mol between 2.4 and 1.6 Å), we observe no global or local minima at short B–F′ distances. For the (CH₃)₂CHF–BF₃ and (CH₃)₃CF–BF₃ potentials in dielectric media, we do observe a distinct flattening along the inner wall, which results in shelf‐like region near 1.7 Å, but this feature is not a true local minimum. We have also obtained low‐temperature infrared spectra of the (CH₃)₂CHF–BF₃ complex in solid neon, and the frequencies agree quite favorably with those obtained via computations, which validates the computational assessment of the gas‐phase complexes. Copyright © 2011 John Wiley & Sons, Ltd.     

Effect of adding Ar gas on the pulse height distribution of BF<Subscript>3</Subscript>-filled neutron detectors

Boron trifluoride (BF₃) proportional counters are used as detectors for thermal neutrons. They are characterized by high neutron sensitivity and good gamma discriminating properties. Most practical BF₃ counters are filled with pure boron trifluoride gas enriched up to 96% ¹⁰B. But BF₃ is not an ideal proportional counter gas. Worsening of plateau characteristics is observed with increasing radius due to impurities in gas. To overcome this problem, counters are filled with BF₃ with an admixture of a more suitable gas such as argon. The dilution of BF₃ with argon causes a decrease in detection efficiency, but the pulse height spectrum shows sharper peaks and more stable plateau characteristics than counters filled with pure BF₃. The present investigations are undertaken to study the pulse height distribution and other important factors in BF₃+Ar filled signal counters for neutron beam applications. Tests are performed with detectors with cylindrical geometry filled with BF₃ gas enriched in ¹⁰B to 90%, and high purity Ar in different proportions. By analysing pulse height spectra, a value of 6.1 ± 0.2 has been obtained for the branching ratio of the ¹⁰B(n,α) reaction.      

Ionic liquid structure: the conformational isomerism in 1‐butyl‐3‐methyl‐imidazolium tetrafluoroborate ([bmim][BF4])

As a probe of local structure, the vibrational properties of the 1‐butyl‐3‐methylimidazolium tetrafluoroborate [bmim][BF₄] ionic liquid were studied by infrared (IR), Raman spectroscopy, and ab initio calculations. The coexistence of at least four [bmim]⁺ conformers (GG, GA, TA, and AA) at room temperature was established through unique spectral responses. The Raman modes characteristic of the two most stable [bmim]⁺ conformers, GA and AA, according to the ab initio calculations, increase in intensity with decreasing temperature. To assess the total spectral behavior of the ionic liquid both the contributions of different [bmim]⁺ conformers and the [bmim]⁺− [BF₄]⁻ interactions to the vibrational spectra are discussed. Copyright © 2008 John Wiley & Sons, Ltd.     

Submillimeter and infrared spectroscopy on La0.85Sr0.15MnO3

The optical conductivity of La_0.85Sr_0.15MnO₃ single crystals was studied by means of submillimeter and infrared spectroscopy for frequencies cm^-1 and temperatures 10 K < T <300 K. The submillimeter conductivity follows the temperature dependence of the dc-data. The phonon spectrum of La_0.85Sr_0.15MnO₃ changes considerably below K revealing a structural phase transition induced by charge or orbital order. At T =10 K a number of phonon modes can be identified in addition to the room-temperature spectrum. The optical conductivity () in the mid-infrared reveals the characteristics of small polaron absorption. Below the magnetic ordering temperature the polaron binding energy is highly reduced, but the onset of charge order interrupts the formation of free charge carriers with a Drude-like behavior. The frequency and temperature dependence of in this regime qualitatively resembles the small polaron predictions by Millis et al. (Phys. Rev. B 54, 5405 (1996)). Received 5 November 1999     

Polar relaxation mode in PbZrO3 crystals

Abstract

In antiferroelectric lead zirconate crystal with one phase transition a nearly monodispersive dipolar relaxation has been found in the paraelectric phase and temperature range 20 K below T _c in the frequency region 20—3 ′ 10⁵ Hz. This relaxation has a dominating influence on the temperature dependence of dielectric susceptibility. Relaxation time obeys the Arrhenius law increasing up to 1.5 ′ 10^?2s (11 Hz) at T _c and then exhibiting a distinct jump.     

Measured and predicted band model parameters of BF3(v3) at high temperatures

Two experimental techniques were used to determine the high temperature infrared absorption coefficients of the v₃ band of BF₃. A high temperature flow tube fitted with a multipass infrared absorption cell was used to determine the BF₃ absorption coefficients at 295, 585, 870, 1150, and 1440K. BF₃ was also used in a flame emission-absorption apparatus to determine the BF₃ absorption coefficients at 2400 K.A generalized formulation for predicting the S/d and 1/d band model parameters of symmetric top perpendicular bands of MX₃ molecules is presented. The effect of including nuclear spin statistics in computing the S/d and 1/d band model parameters is considered. It is shown that nuclear spin statistic?s effect only the 1/d parameter and are significant only for the case of zero nuclear spin. A number of practical considerations, which arise in designing a computer algorithm to calculate the S/d and 1/d parameters, are discussed.Comparisons of the theoretical and experimental BF₃ absorption coefficients are made. Good agreement between theory and experiment at all temperatures was obtained by adjusting only two vibrational energy coupling constants, _χ23 and _χ34. Predicted S/d and 1/d band model parameters at 300, 600, 900, 1200, 1500, 2000, 2500, and 3000 K are presented.     

Synthesis and characterization of hexakis(acetonitrile)chromium(III) tetrafluoroborate, [Cr(NCMe)6][BF4]3. A nonaqueous Cr source

Oxidation of [Cr^II(NCMe)₄][BF₄]₂ with thianthrinium tetrafluoroborate forms [Cr^III(NCMe)₆][BF₄]₃ exhibiting two ν_CN absorptions at 2331 and 2301 cm⁻¹, and has been structurally characterized with an average Cr-N distance of 1.999 Å. From the electronic absorption spectra the ligand field splitting, Δ₀, is 20,160 cm⁻¹, which is slightly larger than [Cr^III(OH₂)₆]³⁺ in accord with the divalent chromium analogues. The 298 K ESR has a resonance at g=1.9884, and the magnetic susceptibility has a 300 K moment of 3.85μ_B characteristic of S=3/2 Cr(III). The field dependence of the magnetization can be fit to the Brillouin function also characteristic of S=3/2.