Bay Functionalized Perylenediimide with Pyridine Positional Isomers: NIR Absorption and Selective Colorimetric/Fluorescent Sensing of Fe<Superscript>3+</Superscript> and Al<Superscript>3+</Superscript> Ions

Bay functionalized perylene diimide substituted with pyridine isomers, (2-pyridine (2HMP-PDI), 3-pyridine (3-HMP-PDI) and 4-pyridine (4-HMP-PDI)) have been synthesized and explored for selective coloro/fluorimetric sensing of heavy transition metal ions. HMP-PDIs showed strong NIR absorption (760–765 nm) in DMF. The absorption and fluorescence of HMP-PDIs have been tuned by make use of pyridine isomers. Reddish-orange color was observed for 2-HMP-PDI (λ_max = 437, 551, 765 nm) whereas 4-HMP-PDI exhibited light green (λ_max = 432, 522, 765 nm). 3-HMP-PDI showed orange-yellow (λ_max = 431, 524, 762 nm). The fluorescence spectra of 2-, 3- and 4-HMP-PDI showed λ_max at 585, 538, 546 nm, respectively. Interestingly, HMP-PDI dyes showed selective color change (intense pink color) and fluorescence quenching for Fe³⁺ and Al³⁺ metal ions in DMF. Absorbance spectra revealed complete disappearance of NIR absorption and intensification/appearance of new peak at lower wavelength. The concentration dependent studies suggest that 4-HMP-PDI can detect up to 36.52 ppb of Fe³⁺ and 43.12 ppb of Al³⁺ colorimetrically. The interference studies in presence of other metal ions confirmed the good selectivity for Fe³⁺ and Al³⁺. The mechanistic studies indicate that Lewis acidic character of Fe³⁺ and Al³⁺ ions were responsible for selective color change and fluorescence quenching.     

FTIR Study of the ν1/ν4 Bands of D3SiCl near 1600 cm

The ν₁ (A₁, 1583.22 cm⁻¹) and ν₄ (E, 1615.33 cm⁻¹) Si-D stretching bands of monoisotopic D₃Si³⁵Cl have been studied by FTIR spectroscopy with a resolution of 3.3×10⁻³ cm⁻¹. We have assigned 2341 rovibrational lines for ν₁ (J_max=70, K_max=19) and 6207 for ν₄ (J_max=75, K_max=27). Both (ΔK=±1, Δ?=±1) and (ΔK=±2, Δ?=?1) interactions connect the v₁=1 and v₄=1 levels, the latter exerting moreover a weak ?(2, 2) interaction. These interactions were taken into account in a nonlinear least-squares fit, refining 29 free parameters with a standard deviation of 0.257×10⁻³ cm⁻¹ over 6722 nonzero-weighted data. Blended lines and about 250 of the 330 lines belonging to the K=11 subband of ν₁ and the KΔK=−6 subband of ν₄ were zero-weighted because they are locally perturbed respectively by the neighboring upper states of the 2ν₃+ν₆ (E, 1561.95 cm⁻¹) and 3ν₃ (A₁, 1604.81 cm⁻¹) bands. Equivalent fits were obtained for altogether three different models obeying constraints according to the theory of unitary equivalent reductions of the rovibrational Hamiltonian. By means of a band contour simulation both the transition moment ratio |M₁:M₄|=0.67 and a positive sign of the Coriolis intensity perturbation were determined.     

Excited state absorption dynamics of fast relaxing dye no. 5

The excited state absorption dynamics of the fast mode-locking dye No. 5 for Nd-glass lasers is investigated. The excited state absorption cross-section σ_ex for 1.053 μm picosecond pulse excitation is determined from energy transmission measurements. The excited state absorption populates a higher lying singlet state S₄. The population lifetime τ₄ of this state is determined from two-step excited fluorescence quantum yield measurements. The obtained values are σ_ex= (5.5±1)×10^-17 cm² and τ₄=60±20 fs.     

Determining the excited‐state substituent constants of furyl and thienyl groups

Six series of styrene derivatives XCH═CHArY (total of 65) containing the styrene parent molecular skeleton were synthesized (here, Y is OMe, Me, H, F, Cl, CF₃, CN, and NO₂, and X is 2‐furyl, 3‐furyl, 2′‐methyl‐2‐furyl, 2‐thienyl, 3‐thienyl, and 2′‐methyl‐2‐theniyl). Their ultraviolet absorption spectra were measured in anhydrous ethanol, and their wavelength of absorption maximum λ_max was recorded. For the wavenumber ν_max (cm^?1, ν_max = 1/λ_max) of the obtained λ_max, a quantitative correlation analysis was performed, and 6 excited‐state substituent constants of groups X were obtained by means of curve‐fitting method. Taking the ν_max values of total 90 compounds of styrene derivatives as a data set (including 25 compounds from reference and 65 compounds of this work), a quantitative correlation analysis was performed, and the reliability of the obtained was verified. In addition, 12 samples of disubstituted Schiff bases (XCH═NArY) involving the above groups X were synthesized, and their ν_max values were recorded. Using these 12 ν_max together with the 14 ν_max values of Schiff bases taken from reference (total of 26 compounds), it was further verified that the values are reliable by means of quantitative correlation method.     

High-resolution FTIR and MMW study of the v4 = 2 (A1, E) excited state of NF3 near 985 cm: the axial ground state rotational constants derived by the “loop-method”

The two substates v₄ = 2⁰ (A₁, 983.702 cm⁻¹) and v₄ = 2^±2 (E, 986.622 cm⁻¹) of the oblate symmetric top molecule, ¹⁴NF₃, have been studied by high-resolution (2.5 × 10⁻³ cm⁻¹) infrared spectroscopy of the overtones and 2ν₄ − ν₄ hot bands. Transitions of the overtone, the hot band, and the previously measured fundamental band were combined to yield 585 ground state combination differences differing in K by ±3, with K_max = 36. Using the “loop-method,” a fit (standard deviation σ = 0.320 × 10⁻³ cm⁻¹) provided a complete set of the hitherto not experimentally known axial ground state constants. In units of cm⁻¹ these have the following values: . Upper state parameters were determined using a vibrationally isolated model. Considering l (2, 2) and l (2, −1) interactions between the v₄ = 2⁰ and v₄ = 2^±2 substates and effects accounting for the l (4, −2) interactions within the kl = −2 levels, 25 upper state parameters were obtained by fitting 2747 IR data (1842 transitions, 905 deduced energies, J_max = 42, K_max = 39) with σ_IR = 0.353 × 10⁻³ cm⁻¹. Moreover, millimeter-wave spectroscopy furnished 86 transitions (J_max = 16, K_max = 13) measured on the v₄ = 2 excited state. A merged fit, refining 24 parameters using the described model gave σ_IR = 0.365 × 10⁻³ cm⁻¹ andσ_MMW = 0.855 × 10⁻⁶ cm⁻¹ (26 kHz). The anharmonicity constants (in cm⁻¹) are x₄₄ = −0.84174 (2) and g₄₄ =  + 0.73014 (1). In addition to this model, the D, Q, and L reductions of the rovibrational Hamiltonian were tested. Standard deviations σ_IR = 0.375 × 10⁻³ cm⁻¹ and σ_MMW = 0.865 × 10⁻⁶ cm⁻¹ were obtained for both D and L reductions, and σ_IR = 0.392 × 10⁻³ cm⁻¹ and σ_MMW = 0.935 × 10⁻⁶ cm⁻¹ for Q reduction. The unitary equivalence of the majority of the 18 tested relations between the derived parameters was satisfactorily fulfilled. This confirms that the v₄ = 2 excited vibrational state can be considered in reasonable approximation to be isolated.     

Spectral manifestations of <Emphasis Type="Italic">d</Emphasis>-π exchange and charge transfer interactions in Cu(II) porphyrins

New absorption bands due to spin-forbidden transitions from the ground state to excited triplet states are found at 295 K in the near-IR absorption spectra of a number of Cu(II) complexes of octaethylporphyrin (OEP) that differ in the nature, number, and position of their side substituents. The frequency distribution, number, and nature of these transitions are analyzed using computer decomposition of complex contours into Gaussian components and additional data from the phosphorescence and phosphorescence excitation spectra (295-77 K). The d-π exchange integrals, determining the energy splitting ΔE = E(²T₁)–E(⁴T₁) in the compounds under study, are calculated on the basis of the experimental data obtained. It is shown that, in addition to the formally spin-allowed ²S₀ → ²T₁ transition (λ_max = 833 nm), the absorption spectrum of the nonplanar CuOETPP molecule at 295 K exhibits the low-intensity spin-forbidden ²S₀ → ⁴T₁ transition (λ_max = 937 nm). For this compound at 77 K, phosphorescence from the ⁴T₁ state is observed (λ_max = 955 nm), with a quantum yield equal to ?_Ph = 0.0015 and a decay time amounting to τ_Ph = 190 ns. For the CuOEP-Ph(o-NO₂) molecule, which contains the electron-acceptor nitro group, direct absorption from the ground state S₀ to a charge transfer (CT) state (λ_max = 845 nm) is observed at 295 K. The extinction coefficient of this absorption and the energy of the CT state are determined.     

Pressure broadening of the NO2 hyperfine multiplet at 93 GHz

Line shapes of the hyperfine NO₂ 26(1,25)←25(2,24) rotational transition have been measured at pressures below 3 torr with a bridge spectrometer originally designed for direct absolute absorption studies. The multiplet consists of six lines with δF=δJ=δN=1 in the vicinity of 93,445 MHz. The same line-broadening parameter of 3.7 MHz/torr and the same maximum absorption of 1.8×10^-5 cm^-1 have been found for all 6 lines. The maximum absorption of the strongly overlapped multiplet at a pressure of 10 torr was measured to be 1.06×10^-4 cm^-1, in good agreement with the theoretical value. The interference effect of the overlapping lines turns out to be below ?10%, so that a simple superposition of lorentzian shapes is a good approximation for this case. The remaining difference can be compensated for by the introduction of an overlap parameter for each line.     

The (ν1, ν4, ν2+ν3, ν3+ν5) Polyad of D3SiF around 1600 cm, Studied by High-Resolution FTIR Spectroscopy

The ν₁ (A₁, 1578.31 cm⁻¹)/ν₄(E, 1615.17 cm⁻¹) Si-D stretching dyad of D₃SiF has been studied by FTIR spectroscopy with a resolution of 2.4×10⁻³ cm⁻¹. Only weak interactions of Coriolis (ΔK=±1, Δ?=±1) and α resonance (ΔK=±2, Δ?=?1) type between ν₁ and ν₄, and of ? (2,−4) type within ν₄, were revealed. However, the v₁=1 and v₄=1 levels were found to be severely perturbed by the v₃=v₅=1 (E, 1590.37 cm⁻¹) and v₂=v₃=1 (A₁, 1604.25 cm⁻¹) states. These perturbations are observable only near level crossings involving strong Coriolis and α interactions. The energy structure within these perturbers is severely complicated by strong Coriolis and α resonances and by ? (2, 2), ? (2,−1), and ? (2,−4) interactions as already revealed by the ν₂(A₁, 710.16 cm⁻¹) and ν₅ (E, 701.72 cm⁻¹) fundamentals. Interactions of the perturbing states with the ν₁/ν₄ dyad are particularly evident in local crossings. In total, 12 transitions belonging to the dark states and 68 perturbation-allowed transitions within the ν₁/ν₄ dyad have been detected among the more than 5000 transitions that have been assigned for the ν₁/ν₄ dyad, with J_max and K_max of 50 and 30, respectively. Altogether about 85% of the assigned transitions were fitted with a standard deviation of 0.221×10⁻³ cm⁻¹, leading to 61 parameters of the interacting polyad.     

Specific features of absorption and luminescence in CsBr: EuOBr crystals

The specific features of the absorption, photoluminescence, x-ray luminescence, thermally stimulated luminescence, and photostimulated luminescence spectra of CsBr: Eu²⁺ single crystals grown using the Bridgman method are investigated in the temperature range 80–500 K at the highest possible dopant content (0.1–0.4 mol % EuOBr in the batch) required for preparing perfect crystals. It is shown that an increase in the dopant content leads to a broadening of the absorption and photoluminescence excitation bands with maxima at wavelengths of 250 and 350 nm due to the interconfigurational transitions 4f⁷(⁸S_7/2) → 4f⁶5d(e _g , t_2g) in Eu²⁺ ions. The photoluminescence and photostimulated luminescence spectra of CsBr: EuOBr single crystals (0.1–0.4 mol % EuOBr) contain a band at a wavelength of λ_max=450 nm and bands at wavelengths of λ_max=508–523 and 436 nm. The last two bands are assigned to Eu²⁺-V_Cs isolated dipole centers and Eu²⁺-containing aggregate centers, respectively. It is revealed that the intensity of the luminescence associated with the aggregate centers (λ_max=508–523 nm) is maximum at an EuOBr content of less than or equal to 0.1 mol % and decreases with an increase in the dopant content. The possibility of forming CsEuBr₃-type nanocrystals that are responsible for the green luminescence observed at a wavelength λ_max=508–523 nm in CsBr: Eu crystals is discussed. The intensity of photostimulated luminescence in the CsBr: EuOBr crystals irradiated with x-ray photons is found to increase as the dopant content increases. It is demonstrated that CsBr: EuOBr crystals at a dopant content in the range 0.3–0.4 mol % can be used as x-ray storage phosphors for visualizing x-ray images with high spatial resolution.     

A new analysis of the ν4(E) rovibrational band of the symmetric top molecule PF3

The high-resolution Fourier transform infrared spectrum of phosphorus trifluoride PF₃ have been reinvestigated in the ν₄ perpendicular band region around 347 cm⁻¹. Thanks to recent pure rotational measurements, 595 new infrared transitions of the ν₄ band have been assigned extending the rotational quantum number values up to K_max = 66 and J_max = 67. As a consequence of this extension, a sophisticated model containing a large number of parameters and interaction constants was adopted for the analysis of the IR transitions of the ν₄ fundamental band of PF₃. A merge of the IR transitions and the reported MW/MM/RF data within the v₄ = 1 excited level yielded an accurate rotational ground state C₀ value, 0.159970436 (69) cm⁻¹, which was used to determine an improved GS structure, r₀(P-F) = 1.56324405 (11) Å and ?(FPF) = 97.752232 (29)°. All experimental data have been refined applying various reduction forms of the effective rovibrational Hamiltonian developed for an isolated degenerate state of a symmetric top molecule. The v₄ = 1 excited state of the PF₃ oblate molecule was treated with models taking into account ?- and k-type intravibrational resonances. Parameters up to sixth order have been accurately determined and the unitary equivalence of the derived parameter sets in different reductions was demonstrated.     

Extended Analysis of Line Positions and Intensities of Ozone Bands in the 2900-3400 cm Region

The 2900-3400 cm⁻¹ spectral range is revisited for an accurate determination of line positions and line intensities of the 3ν₃, ν₁+2ν₃, 2ν₁+ν₃, and 3ν₁ bands of ozone. The fit on 4520 rotational energy levels of (012), (111), (210), (130), (003), (102), (201), and (300) vibrational states determined from observed transitions of cold and hot bands in the 2400-3400 cm⁻¹ region with J_max=65 and K_{a max}=20 gives a r.m.s.=7×10⁻⁴ cm⁻¹ and provides a satisfactory agreement between calculated and observed line positions (dimensionless standard deviation is χ=1.44). The set of 2580 line intensities of 7 rovibrational bands has been measured and fitted with a r.m.s.=6.9% (χ=1.2), leading to the determination of transition moment parameters for these bands. Using these parameters we have obtained more precise estimation for the integrated band intensities S(3ν₃)=1.41×10⁻¹⁹, S(ν₁+2ν₃)=1.28×10⁻²⁰, S(2ν₁+ν₃)=7.91×10⁻²¹, S(3ν₁)=4.72×10⁻²² cm⁻¹/mol cm⁻² at 296 K, with a cutoff 2×10⁻²⁶ cm⁻¹/mol cm⁻². The interactions of the tetrad (003)/(102)/(201)/(300) with the (130) state and the tetrad (040)/(012)/(111)/(210) are studied.     

Half-life and magnetic moment of the 1+ first excited state in116Sb

The life-time and the magnetic dipole moment of the 1⁺ isomeric state in¹¹⁶Sb have been measured by the TDPAD method. The state was populated in the reaction¹¹⁶Sn(p, n)¹¹⁶Sb atE _p =15 MeV. The obtained results,μ(1⁺,¹¹⁶Sb)=+2.47(9) n.m. andT _1/2= 194(4) ns, support the pure single particle [πd _5/2*vd _3/2] configuration for the 1⁺ isomeric state.     

Nuclear hyperfine structure in the XΣ state of ZrC

Electronic band systems of zirconium monocarbide, ZrC, in the 16 000-19 000 cm⁻¹ region have been observed following the reaction of laser-ablated Zr atoms with methane under supersonic free-jet conditions. Rotational analyses of high-resolution spectra have shown that the ground state of ZrC is a ³Σ state, with r₀=1.8066 Å and an unexpectedly small spin-spin parameter, λ=0.5139 cm⁻¹. The spectra are dense because of the five naturally occurring isotopes of Zr. Four of these, with mass numbers 90, 92, 94, and 96, have I=0, but the fifth, ⁹¹Zr, present in 11.22% abundance, has I=5/2. Lines of ⁹¹ZrC can be assigned in some of the strongest bands, and are found to display sizeable hyperfine splittings, with widths of up to 0.2 cm⁻¹. Analysis shows that the largest hyperfine effects are in the ground state, where b=−0.03133±0.00015 cm⁻¹ and c=−0.00123±0.00037 cm⁻¹ (3σ error limits). The large Fermi contact parameter, b, indicates that an unpaired Zr 5sσ electron is present, which, taken together with the small value of λ, means that the ground state must be a ³Σ⁺ state, from the electron configuration (Zr 5sσ)¹ (C 2pσ)¹. Internal hyperfine perturbations occur between the F₁ and F₃ electron spin components of the ground state in the range N=2-4, producing extra lines in some of the branches; the perturbations are of the type ΔN=0, ΔJ=±2, and are a second-order effect arising because the F₁ (J=N+1) and F₃ (J=N−1) spin components both interact with the F₂ (J=N) component through ΔN=0, ΔJ=±1 matrix elements of the Fermi contact operator. Second-order perturbations of this type can only occur in states that are very close to case (b) coupling.     

EPR and optical absorption studies of Fe ions in sodium borophosphate glasses

Electron paramagnetic resonance (EPR) and optical absorption spectral investigations have been carried out on Fe³⁺ ions doped sodium borophosphate glasses (NaH₂PO₄-B₂O₃-Fe₂O₃). The EPR spectra exhibit resonance signals with effective g values at g=2.02, g=4.2 and g=6.4. The resonance signal at g=4.2 is due to isolated Fe³⁺ ions in site with rhombic symmetry whereas the g=2.02 resonance is due to Fe³⁺ ions coupled by exchange interaction in a distorted octahedral environment. The EPR spectra at different temperatures (123-295 K) have also been studied. The intensity of the resonance signals decreases with increase in temperature whereas linewidth is found to be independent of temperature. The paramagnetic susceptibility (χ) was calculated from the EPR data at various temperatures and the Curie constant (C) and paramagnetic Curie temperature (θ_p) have been evaluated from the 1/χ versus T graph. The optical absorption spectrum exhibits bands characteristic of Fe³⁺ ions in octahedral symmetry. The crystal field parameter (Dq) and the Racah interelectronic repulsion parameters (B and C) have also been evaluated and discussed.     

Ground state parameters of BiH3 from infrared and millimeter-wave spectra: ground state and equilibrium structures

Unstable, short-lived BiH₃ has been synthesized and investigated by rotational spectroscopy in the range 158 (J=1-0) to 1280 GHz (J=8-7). Quadrupole and spin-rotation hyperfine structures (eQq=584.676(96) MHz), and the A₁A₂ splitting of the K=3 ground state level, have been resolved. By merging the pure rotational data with 1764 ground state combination differences obtained from the analysis of high resolution Fourier transform infrared spectra of the ν₁-ν₄ bands [J. Mol. Spectrosc. (2004) (in press)] spanning J and K values up to 16 and 14, respectively, with 0?ΔK?9, the ground state rotational and centrifugal distortion constants up to octic and sextic terms for reductions A and B, respectively, have been determined. Of the reductions of the ground state rovibrational Hamiltonian, reduction B including ε rather than h₃ as off-diagonal element is clearly favored. An experimental r₀ structure of the very-near spherical oblate symmetric top BiH₃, r(BiH)=178.82 pm and α(HBiH)=90.320°, has been deduced from the rotational constants B₀=2.64160172(18) and C₀=2.6010403(31) cm⁻¹. The derived experimental r_e structure, r_e(BiH)=177.834(50) pm and α_e(HBiH)=90.321(10)°, was determined. This is in excellent agreement with the most recent ab initio structure, r_e(BiH)=177.84 pm, and α_e(HBiH)=90.12°.     

Line shape and excitation strength of the first excited state in9Be

The line shape and the excitation strength of the very weak first excited J ^π =1/2⁺ state at E_x=1.684 MeV in Zeitschrift für Physik Zeitschrift für Physik⁹Be has been investigated with high-resolution inelastic electron scattering at E₀=45 and 49 MeV and scattering angles θ=105°, 117°, 129° and 165°, and with high-resolution inelastic proton scattering at E₀=13MeV and θ=15° and 18°. Due to lying just above the neutron threshold the level has a strongly asymmetric line shape which in both experiments can be described consistently with a Breit-Wigner expression modified on the low energy side by the threshold behaviour of the cross section. The resonance energy is E_R=1.684 ± 0.007 MeV and the width T=217± 10 keV in thec.m. system. A single particle potential model calculation reproduces the line shape and the resonance parameters fairly well. In addition, the inelastic electron scattering form factor has been measured. In the range of momentum transfersq =0.24-0.46 fm^?1 it is dominated by a 0p_3/2→ 1s_1/2 particle-hole transition. The transition is mainly longitudinal and of isoscalar nature with a strength of B (E1)↑ =0.027 + 0.002 e² fm², but a small M2 contribution ofB(M2)↑=8.8 ±1.5 μ _N ² fm² has also been detected.     

High resolution FTIR spectroscopy of pentafluoroethane: perturbations in the Coriolis doublet of ν4 and ν13

The FTIR spectrum of pentafluoroethane (R125) was measured in the mid infrared region from 900 to 4000 cm⁻¹. Vibrational assignments for R125 are revised by comparison of previous and current experimental data with ab initio calculations at both the MP2/6-311+(d,p) and B3LYP/TZV+(3df,3p) levels of theory. High resolution FTIR spectra were recorded at room temperature and in an enclosive flow cell at a rotational temperature of 140 K. The cold spectrum was sufficiently resolved to enable rovibrational analyses of the overlapping ν₄ (1200.7341 cm⁻¹) and ν₁₃ (1223.3 cm⁻¹) bands, which have a/c hybrid and b-type character, respectively. Ground state combination differences were used to confirm assignment of 2375 lines to ν₄ (J_max = 86, K_{a max} = 50) and 2921 lines to ν₁₃ (J_max = 60, K_{a max} = 54). Effective rotational and centrifugal distortion constants were determined for ν₄, and the polarization ratio was found to be . Severe Coriolis perturbations prevent any satisfactory fit to the ν₁₃ band.     

Spin state and exchange in the quasi-one-dimensional antiferromagnet KFeS2

We report the optical spectra and single crystal magnetic susceptibility of the one-dimensional antiferromagnet KFeS₂. Measurements have been carried out to ascertain the spin state of Fe³⁺ and the nature of the magnetic interactions in this compound. The optical spectra and magnetic susceptibility could be consistently interpreted using aS=1/2 spin ground state for the Fe³⁺ ion. The features in the optical spectra have been assigned to transitions within thed-electron manifold of the Fe³⁺ ion, and analysed in the strong field limit of the ligand field theory. The high temperature isotropic magnetic susceptibility is typical of a low-dimensional system and exhibits a broad maximum at ∼565K. The susceptibility shows a well defined transition to a three dimensionally ordered antiferromagnetic state atT _N=250 K. The intra and interchain exchange constants,J andJ′, have been evaluated from the experimental susceptibilities using the relationship between these quantities, andχ _max,T _max, andT _N for a spin 1/2 one-dimensional chain. The values areJ=−440.71 K, andJ′=53.94 K. Using these values ofJ andJ′, the susceptibility of a spin 1/2 Heisenberg chain was calculated. A non-interacting spin wave model was used belowT _N. The susceptibility in the paramagnetic region was calculated from the theoretical curves for an infiniteS=1/2 chain. The calculated susceptibility compares well with the experimental data of KFeS₂. Further support for a one-dimensional spin 1/2 model comes from the fact that the calculated perpendicular susceptibility at 0K (2.75×10⁻⁴ emu/mol) evaluated considering the zero point reduction in magnetization from spin wave theory is close to the projected value (2.7×10⁻⁴ emu/mol) obtained from the experimental data.     

Complex permittivity, permeability and microwave absorbing properties of (Mn2−xZnx)U-type hexaferrite

Complex permittivity, permeability and microwave absorbing properties of a U-type hexaferrite series Ba₄Mn_(2−x)Zn_xFe₃₆O₆₀ (with 0≤x≤2 in step of 0.5) have been examined in the X-band (8.2-12.4 GHz) frequency range. The series have been prepared using conventional solid state reaction route. Microstructural variations with composition have been found with X-ray diffraction (XRD) and scanning electron microgram (SEM). The complex permittivity (ε^?=ε′−jε″) and permeability (μ^?=μ′−jμ″) were measured using vector network analyzer (Agilient Make model PNA E8364B). These parameters were then used for calculating the reflection loss for determination of microwave absorbing properties. Addition of Zn resulted in an increase in reflection loss from −4 dB (or 60 % absorption) in sample with x= 0 to −32 dB (99.92% absorption) in sample with x=1 when the sample thickness was 1.7 mm. Multiple peaks of resonance were obtained in the dielectric and magnetic loss spectra for all samples with x>0. The result indicates that the sample with composition Ba₄MnZnFe₃₆O₆₀, i.e., x=1, can be used effectively for microwave absorption and suppression of electromagnetic interference.     

High-resolution infrared and millimeterwave spectra of the v3=1 vibrational state of NF3 at 907 cm

The ν₃^±1 perpendicular band of ¹⁴NF₃ ( cm⁻¹) has been studied with a resolution of 2.5 × 10⁻³ cm⁻¹, and 3682 infrared (IR) transitions (J_max=55, K_max=45) have been assigned. These transitions were complemented by 183 millimeterwave (MMW) rotational lines (J_max=25, K_max=19) in the 150–550 GHz region (precision 50–100 kHz). The kl=+1 level reveals a strong A₁/A₂ splitting due to the l(2,2) rotational interaction (q=−4.05 × 10⁻³ cm⁻¹) while the kl=−2 and +4 levels exhibit small A₁/A₂ splittings due to l(2,−4) and l(0,6) rotational interactions. All these splittings were observed by both experimental methods. Assuming the v₃=1 vibrational state as isolated, a Hamiltonian model of interactions in the D reduction, with l(2,−1) rotational interaction (r=−1.96 × 10⁻⁴ cm⁻¹) added, accounted for the observations. A set of 26 molecular constants reproduced the IR observations with σ_IR=0.175 × 10⁻³ cm⁻¹ and the MMW data with σ_MMW=134 kHz. The Q reduction was also performed and found of comparable quality while the QD reduction behaved poorly. This may be explained by a predicted Coriolis interaction between v₃=1 and v₁=1 (A₁, 1032.001 cm⁻¹) which induces a slow convergence of the Hamiltonian in the QD reduction but has no major influence on the other reductions. The experimental equilibrium structure could be calculated as: r_e(N–F)=1.3676 Å and (FNF)=101.84°.