Selenium dioxide: Vibrational analysis of the 3130 Å1B2-X̃1A1 absorption system

The B absorption system of the three isotopic species ⁷⁸Se¹⁶O₂, ⁸⁰Se¹⁶O₂, and ⁷⁸Se¹⁸O₂ have been comparatively studied in the vapor phase. The 0_0⁰ band is at 31955.0/31957.4/31963.9 cm^?1, respectively. The main vibrational structure is due to 1_0ⁿ2_0^m progressions, with maximum intensity at n ～ 6. The stronger progressions are those with m = 0, 1, 2, 3. The progressions are severely perturbed. The molecule is bent in both of the combining electronic states. In the ground state for the (80, 16) species, ν₁″(a₁) = 922.6, ν₂″(a₁) = 372 cm^?1. In the electronically excited state, identified as ¹B₂, ν₁′, and ν₂′ have the approximate values 649 and 258 cm^?1, respectively. Evidence is presented in favor of a double-minimum potential function with respect to Q₃′, the band 3_0¹ being observed with appreciable intensity. The height of the potential barrier is about 600 cm^?1.     

Observation of the c3Πu-X1Σg+ intersystem transition in the absorption spectrum of P2

The observation of the c³Π_u-X¹Σ_g⁺ intersystem transition of P₂ is reported. The 6-0 band of the system was identified on high resolution absorption plates teken on the NRC 10-m vacuum spectrograph at Ottawa. A rotational analysis of the band is given together with that of the adjacent 5-0 band of the C¹Σ_u⁺-X¹Σ_g⁺ system, the upper level of which is involved in a mutual perturbation with the c³Π_u, v = 6 level. The interaction parameters for the perturbation are derived. It is proposed that the appearance of the 6-0 band of the c³Π_u-X¹Σ_g⁺ transition is due to intensity borrowing from the strong, allowed C¹Σ_u⁺-X¹Σ_g⁺ system. Accurate values for the energies of the c³Π_u, b³Π_g, and a³Σ_u⁺ states relative to the ground state are given. The analysis of two other bands, 2-0 and 7-0, of the C¹Σ_u⁺-X¹Σ_g⁺ system whose upper levels likewise interact strongly with the c³Π_u state are also given.     

Anisotropy of hexagonal ferrites with M,W and Y structures containing Fe3+ and Fe2+ as magnetic ions

The ferrimagnetic saturation moment and hexagonal anisotropy constant K₁ have been measured at 4K on a Zn₂Y single crystal and on polycrystalline BaFe²⁺₂W and SrFe²⁺₂W samples. The moment of Fe₂W is in agreement with a collinear spin coupling and with the known site occupation for the Fe²⁺ ions. The moment of Zn₂Y is 9% lower than the value for a collinear configuration.The uniaxial anisotropy of Fe²⁺ in hexagonal ferrites is discussed and compared with that of Co²⁺. No noticeable Fe²⁺ anisotropy is found in Fe₂W in contrast to LaM = LaFe²⁺Fe³⁺₁₁O₁₉, in which the Fe²⁺ anisotropy is strong. The difference is attributed to the symmetry difference of the sites occupied by the Fe²⁺ ions in both compounds. The current theory does not satisfactorily explain the anisotropy and quadrupole splitting of Fe²⁺ in LaM. From this it is concluded that admixing of ⁵E states and (or) the influence of a dynamical Jahn-Teller effect cannot be neglected.The dipole-dipole anisotropy is computed for the M, W and Y structure and some deviation from the literature data is found. Using these results, a mean anisotropy of 1.3 to 2.3 cm^?1 per Fe³⁺ ion is found for the three structures.     

Fourth-order spin Hamiltonian terms for Fe2+ in rutile structure antiferromagnet FeF2

The paper deals with the spectroscopic and magnetic properties of Fe²⁺ ions in FeF₂. The microscopic spin Hamiltonian theory for Fe²⁺ in crystalline environments with second-kind orthorhombic symmetry is considered. Explicit formulas for the parameters B₀⁽²⁾(D),B₂⁽²⁾(E), g_x, g_y, g_z and, for the first time in the literature, the fourth-order parameters B₀⁽⁴⁾, B₂⁽⁴⁾ and B₄⁽⁴⁾, are derived. Using semi-empirical data for the ⁵D-term energy levels of Fe²⁺ ion in FeF₂, the pressure dependence of the parameters B_q^(k) in the region from 0 to 133 kbar is discussed. The relative role of the fourth-order parameters with respect to the second-order ones is found to increase strongly with pressure (e.g. in the region studied, D increases only by a factor of 3, whereas B₀⁽⁴⁾ increases by a factor of nearly 20). The magnetocrystalline anisotropy of FeF₂; is considered in the strong anisotropy model taking into account the fourth-order spin Hamiltonian terms. The uniaxial anisotropy constants K₁ and K₂ are derived theoretically and their pressure dependence is discussed quantitatively. The theory and numerical results of this paper are useful with regard to Fe²⁺ in other isomorphic fluorides, namely: MgF₂, ZnF₂, VF₂ and MnF₂. It is found that the fourth-order spin Hamiltonian parameters are accessible to experimental detection from spectroscopic studies on Fe²⁺ in non-magnetic fluorides and magnetic studies on Fe²⁺ : MnF₂ and FeF₂, preferably under high pressure.     

EPR study of clusters of rare-earth ions in mixed fluoride crystals

The EPR spectra of the (BaF₂)_{1 ? x} (CeF₃) _x system are studied for the concentrations x = 0, 0.001, 0.002, 0.005, 0.01, and 0.02. The appearance of new tetragonal centers is detected beginning from x = 0.002, the intensity of these centers being maximal at x = 0.01. The (CaF₂)_{1 ? x ? y} (CeF₃) _x (YF₃) _y double solutions with x = 0.001 and y from 0 to 0.02 are also studied. In addition to the ordinary tetragonal center, beginning from y = 0.001, a new tetragonal center appears with the same structure as in the previously studied mixed crystals based on BaF₂—namely, the Ce³⁺-□-R³⁺ chain elongated along the fourfold axis substitutes the Ca²⁺-Ca²⁺-Ca²⁺ and Ba²⁺-Ba²⁺-Ba²⁺ chains in regular CaF₂ and BaF₂ crystals (□ is the cation vacancy, and R³⁺ is the Ce³⁺, La³⁺, or Y³⁺ trivalent ion).     

4 T 2→4 A 2 transition in the luminescence spectra of Mn4+ ion in gadolinium gallium garnet at intense laser pumping

The Mn^{4+ 4} T ₂→⁴ A ₂ transition was observed in the luminescence spectrum of Gd₃Ga₅O₁₂:Mn⁴⁺ at intense laser pumping. It is shown that the ⁴ T ₂ → ⁴ A 2 transition becomes more intense than ² E→⁴ A ₂ because of an increase in the role of induced transitions with increasing pump power. This process is most efficient in the region of strongest overlap between the ² E→⁴ A ₂ and ⁴ T ₂→⁴ A ₂ bands, where it leads to strengthening of the zero-phonon line of the latter at 694 nm. It is assumed that GGG:Mn⁴⁺ can be used as an active material in tunable lasers.     

The ν3 band of CD3I around 500 cm−1

The region of the lowest fundamental band ν₃ of CD₃I around 500 cm^?1 is studied at a resolution of 0.015 cm^?1. The K structure in the parallel band ν₃ is resolved for K = 6 – 14. Molecular constants for the ν₃ level are derived, including α₃^A = 3.055(13) × 10^?3 cm^?1. The “hot” band 2ν₃-ν₃ is also investigated.     

AB initio calculations of the electronic properties of N4− in KN3

The energies of the ground state and low-lying excited states of the N₄^? defect in KN₃ have been calculated using ab initio techniques. A rectangular equilibrium geometry with dimensions X = 2.76 and Z = 2.47 a.u. and ground state symmetry of Γ₄⁺ was determined by calculating N₄^? as a free radical. For this ground state the unpaired electron is in a π orbital which is consistent with the experimental hyperfine tensor only if one edge of the N₄^? radical is parallel to the c axis in KN₃. These results were used to calculate the X²Γ₄⁺ state of N₄^? in the crystal field of KN₃, yielding an energy of ?217.899 Hartrees. The isotropic hyperfine constant was calculated to be a = 2.1 G and the components of the anisotropic hyperfine tensor as B_xx = ?3.4 G, B_yy = 7.0 G and B_zz = ?3.6 G, in good agreement with experimental and INDO results. Several excited states were calculated for the N₄^? defect in KN₃. When an estimate was made of the correlation energy, the transition energy of the X²Γ₄⁺→A²Γ₃^? transition agreed well with the peak energy of the 780 nm absorption band which has been attributed to N₄^?.     

Application of atom-photon coincidence techniques to the determination of the differential cross section for excitation ofK(42 P) in low-energy K-N2, CO collisions

The differential cross section for the processK(4² S)+N₂, CO→K(4² P)+ N₂, CO is presented for reduced scattering angles τ<2·10⁴ eV deg. The inelastic process is identified by determining the time-correlation between the inelastically scattered potassium atom and the emittedK(4² P→4² S)photon. The performance of different coincidence techniques is compared. From the differential cross sections values for the position of the curve crossing responsible for the excitation process are derived (R _c=2.77, 2.48 Å andV(R _c )=0.55, 1.00 eV for K-N₂, CO respectively). The values indicate that the lowest ionic intermediate state of the form K⁺-N ₂ ^? , CO^? is responsible for the excitation process.     

Crystal field contribution to Mössbauer isomer shift

The crystal field hamiltonian H_c = B₂⁰Y₂⁰ + B₂²(Y₂² + Y₂^?2) commonly used in the study of electron-spin resonance is employed to obtain new contributions to the ⁵⁷Fe³⁺ isomer shift in the Mössbauer effect. A numerical estimate of the shift is also presented.     

The far-infrared spectrum of tetrahydrothiophene: The bend/twist vibrations and associated barriers

The far-infrared spectrum of tetrahydrothiophene is reinvestigated with a resolution of 0.12 cm^?1 in the region of 50–350 cm^?1. In addition to the bend transitions (ν_b) below 120 cm^?1 reported previously, a number of sequences revealed by the improved resolution are observed for the first time and assigned to transitions of 2ν_b, of the twist (ν_t), and of difference combinations (ν_t - ν_b). Simple one-dimensional modeling of the twist sequence, which is derived from a self-consistent bend-twist energy level diagram, with a quadratic-quartic Hamiltonian suggests a barrier to planarity on the order of 4250 cm^?1. A two-dimensional potential function in the dimensionless coordinates is found to be V(q_b, q_t) = ?249.6q_b² + 4.48q_b⁴ ? 215.5q_t² + 2.73q_t⁴ + 7.00q_b²q_t².     

Comparative study of the semiempirical three-parameter potential energy functions for diatomic molecules

A comparative study is made of four three-parameter semiempirical potential energy functions for 32 electronic states of diatomic molecules and their ions:n ₂:X¹gS _g ⁺ ,B ³π_g,A ³ gS_u,C ³ _u,B′ ³ gS_u.a ¹ π_g, a′gS _u ^? ,Ω ¹δ_u N ₂ ⁺ :X ² gS _g ^gS +A ² π,C ² gS _u ⁺ ,B ² gS _u ⁺ CO:X¹gS⁺,a ³ π, a′³ gS_u,e ³ gS^?,d ³gD₁,A ¹π CO⁺:X²gS⁺,A ² π,B ²gS⁺ O₂:X³gS _g ^? ,B ³ gS_u,c ¹ gS _u ^? ,b ¹gS _g ^s ,a ¹ δ_g,c ³ δ_u O ₂ ⁺ :X ²π_g,A ² π_g, a¹ π_g,b ⁴ gS _g ^? A program for numerically integrating the radial Schrödinger equation by the Cooley method is worked out. Certain additional units are introduced to conserve computer time. The resulting vibrational levels are compared with the experimental levels for all the electronic states studied. It is concluded on the basis of this analysis that it is not possible to describe equally well all the electronic states of various molecules on the basis of any single three-parameter potential function. A method for choosing a potential function for describing some particular electronic state of a diatomic molecule is proposed.     

The millimeter-wave spectrum of chlorosilane

The millimeter-wave spectra of six isotopic species of SiH₃Cl in the ground vibrational states, and of ²⁸SiH₃³⁵Cl in the ν₃ state, have been measured; B_v, D_J, D_JK, and eQq values were obtained. The ν₆ states of ²⁸SiH₃³⁵Cl and ²⁸SiH₃³⁷Cl have also been measured, and B₆, D_J, D_JK, η_J, and |q₆⁺| determined. The l-resonance in this state is very small and A(1 ? ζ) could not be determined. The constants obtained compare well with the less-precise values from high-resolution infrared spectra; the complementary nature of the information from mm-wave and infrared spectroscopy is discussed.     

Infrared rotation-vibration spectra of ethane: The perpendicular band, ν7, of C2H6

The study of the gas-phase infrared spectrum of C₂H₆ in the region of the perpendicular CH-stretching band, ν₇, near 3000 cm^?1 is extended for the ΔK = + 1 subbands as far as K = 20. The spectral resolution of ～0.030 cm^?1 is increased to ～0.015 cm^?1 by deconvolution. The earlier investigation of this band for KΔK = +9 to ?5, is repeated with greater accuracy, providing more reliable ground-state constants (cm^?1): B₀ = 0.663089 ± 24, D₀^J = (0.108 ± 4) × 10^?5, D₀^JK = (0.50 ± 7) × 10^?5. The molecular constants (cm^?1) for the ν₇ fundamental are B₇ = 0.66310 ± 3, A₇ = 2.682, ν₀ = 2985.39, ζ₇ = 0.128. A discussion of resonance effects in this band, in particular x-y-Coriolis and Fermi resonance, is given.     

UV and VUV spectroscopic study of Na0.4Y0.6F2.2 crystals doped with rare-earth ions

The short-wavelength transmission spectra of Na_0.4 R _0.6F_2.2 crystals with R = Y, Yb, or Lu have been investigated. For these crystals, the VUV transmission cutoffs are 78750, 58820, and 75200 cm^?1, respectively. The 4f ⁿ–4f ^n?15d absorption and excitation spectra of Na_0.4Y_0.6F_2.2 crystals activated with Ce³⁺, Pr³⁺, Nd³⁺, Er³⁺, Tm³⁺, and Yb³⁺ ions have been analyzed in the range 30000–80000 cm^?1. The energy positions of the lowest levels of the 4f ^n?15d configurations of these ions in the fluorite crystal matrix Na_0.4Y_0.6F_2.2 are determined. The absorption band in the spectral range 60600–70000 cm^?1 in Na_0.4(Y, Yb)_0.6F_2.2 crystals is due to the charge transfer from F^? to Yb³⁺. It is shown that the environmental symmetry of Ce³⁺ ions in Na_0.4R_0.6F_2.2 (R = Y, Yb, Lu) crystals is almost identical.     

Magnetic anisotropy and saturation of LaFe12O19 and some related compounds

The saturation magnetization σ_s and uniaxial anisotropy constants K₁ and K₂ are measured on a polycrystalline, crystal-oriented sample of LaFe₁₂O₁₉ contaminated with known amounts of Fe₃O₄ and LaFeO₃. K₁ and K₂ increase strongly with decreasing temperature and the value of K₁ = (19–24) × 10⁵ erg/g at T = 0 shows that the substance is considerably more anisotropic than BaFe₁₂O₁₉ (K₁ ? 8·5 × 10⁵ erg/g) at low temperatures. The σ_s-T curve is more convex than that of BaFe₁₂O₁₉, so that σ_s is 11 per cent higher at room temperature but lower at T = 0. The value σ_s(T = 0) = 96·2 G cm³/g (19·2 μ_B/molecule) and the anisotropic behaviour are attributed to the presence of 1 Fe²⁺/molecule occupying the octahedral 2a sites in the magnetoplumbite lattice and having a uniaxial anisotropy of 10–15 cm^?1/ion.From measurements on polycrystalline, crystal-oriented samples of BaFe_10·8Fe²⁺_0·6Ti⁴⁺_0·6O₁₉ and BaFe_10·5Fe²⁺_1·0Sb⁵⁺_0·5O₁₉ it was found that, in comparison with LaFe₁₁Fe²⁺O₁₉, σ_s (T = 0) is smaller and K₁ is much smaller and much less temperature-dependent. The difference in anisotropic behaviour is attributed to a different distribution of the Fe²⁺ ions among the lattice sites due to the effective positive charge of the Ti⁴⁺ and Sb⁵⁺ ions.     

Measurement of the rate of ν e+d → p+p+e − interactions produced by 8B solar neutrinos at the Sudbury Neutrino Observatory

Solar neutrinos from the decay of ⁸B have been detected at the Sudbury Neutrino Observatory (SNO) via the charged current (CC) reaction on deuterium and by the elastic scattering (ES) of electrons. The CC reaction is sensitive exclusively to ν _e, while the ES reaction also has a small sensitivity to ν _μ and ν _τ. The flux of ν _e from ⁸B decay measured by the CC reaction rate is φ ^CC(ν _e )=[1.75±0.07(stat.) _?0.11 ^+0.12 (syst.)×0.05(theor.)]×10⁶cm^?2s^?1. Assuming no flavor transformation, the flux inferred from the ES reaction rate is φ ^ES(ν _x )=[2.39±0.34(stat.) _?0.14 ^+0.16 (syst.)]×10⁶cm^?2s^?1. Comparison of φ ^CC(ν _e) to the Super-Kamiokande collaboration’s precision value of φ ^ES(ν _x) yields a 3.3σ difference, assuming the systematic uncertainties are normally distributed, providing evidence that there is a nonelectron flavor active neutrino component in the solar flux. The total flux of active ⁸B neutrinos is thus determined to be (5.44±0.99)×10⁶ cm^?2 s^?1, in close agreement with the predictions of solar models.     

Absolute intensity measurements of the CO2 bands 401III←000 and 411III←010

The absolute intensities of the transitions 401_III←000 and 411_III←010 of CO₂ have been measured from spectra obtained under high resolution. Both the vibration-rotation line intensities and the integrated band intensities are reported. The rotationless transition moment of 401_III←000 is deduced and a vibration-rotation interaction factor F(m) = 1+(4.92×10^?4)m+(4.4×10^?7)m² is determined. The values obtained are: S_Band(401_III←000) = (25.54±0.22)×10^?5 cm^?2atm_{(293 K)}^?1, |R₀₀₀^401_III| = (1.87±0.02)×10^?4D, and S_Band(411_III←010) = (1.83±0.13)×10^?5 cm^?2atm_{(293 K)}^?1.     

Quantum beats in two-photon resonance fluorescence

The two-photon resonance fluorescence spectrum of a three-level atom is shown to consist of the low frequency modes in addition to the high frequency ones in the limit of high photon densities. The spectral function for the low frequency modes consists of two lorentzian lines describing: the peak occuring at the renormalized beat frequency Δ₊ and that of the zero-photon excitation at the frequency Δ_-, where Δ_±=Δ-3Ω²/2ω_a±Ω²u/2ω_a, u²=1+(2Δω_a/Ω ²)². Here, 2Δ is the energy splitting between the two excited states, ω_a is the photon energy of the pump field and Ω is the Rabi frequency. The peak at the renormalized beat frequency Δ₊ occurs provided that the condition (2Δω_a/Ω²)² > 1 is satisfied. The two-photon laser spectroscopy is expected to be a useful tool for the observation of the low frequency modes in question.