High-Resolution Survey of the Visible Spectrum of NiF by Fourier Transform Spectroscopy

High-resolution spectra of NiF have been recorded in emission by Fourier transform spectroscopy using a very stable discharge source. The 0-0 bands of 14 electronic transitions have been studied, 6 of them for the first time. This work confirms the presence of 5 low-lying spin components X²Π_3/2, [0.25]²Σ⁺, [0.83]A²Δ_5/2, [1.5]B²Σ⁺, and [2.2]A²Δ_3/2 as known from previous laser-induced fluorescence experiments. Eight electronic states are now identified in the 18 000-24 000 cm⁻¹ range above the ground X²Π_3/2 state. Electronic assignments for these excited states are not always obvious because of violations of the selection rules and unusual fine structure parameters. We think that some of the upper states are spin components of quartet states. In such a congested spectrum, high-resolution spectra are best analyzed in conjunction with an energy level diagram constructed mainly by dispersed low resolution laser-induced fluorescence.     

Spectroscopy of nickel chloride: Identification of the [15.0] Π3/2 and [15.0] Δ5/2 states

Vibrational bands belonging to the [15.0] ²Δ_5/2-A²Δ_5/2, [15.0] ²Δ_5/2-X²Π_3/2, and [15.0] ²Π_3/2-X²Π_3/2 electronic transitions of NiCl have been observed in the 14 000-16 000 cm⁻¹ region. The [15.0] ²Δ_5/2 and [15.0] ²Π_3/2 states are identified for the first time. The observed bands have been recorded at high spectral resolution using several techniques, which include intracavity laser spectroscopy (ILS), Fourier transform emission spectroscopy (FTS), and laser induced fluorescence (LIF) spectroscopy. For the ILS absorption spectra, NiCl molecules were produced in a nickel hollow cathode operated with a small amount of CCl₄. For the FTS emission spectra, excited NiCl molecules were produced in a King-type carbon tube furnace loaded with NiCl₂ and heated to 1600 °C. In the LIF work, NiCl molecules were produced by reacting laser-ablated nickel with PCl₃ seeded in argon. Detailed analysis of rotational transition lines indicates that the observed [15.0] ²Δ_5/2 and [15.0] ²Π_3/2 states are only separated by 10 cm⁻¹ and are interacting with each other. Molecular constants for these newly observed electronic states are reported.     

The laser-induced fluorescence spectroscopy of TiF in the ultraviolet region

The laser-induced fluorescence (LIF) spectrum of jet-cooled ⁴⁸TiF has been obtained in the wavelength region of 245-270 nm for the first time. Six pairs of vibronic bands were observed and assigned to two new transitions [37.8]⁴Φ-X⁴Φ and ⁴Δ-X⁴Φ. Rotational analysis was carried out for the (ν′ = 0-3 to ν″ = 0) vibrational bands of the [37.8]⁴Φ_3/2-X⁴Φ_3/2 and [37.8]⁴Φ_5/2-X⁴Φ_5/2 subbands, and also, the (ν′, 0) and (ν′+1, 0) vibrational bands of the ⁴Δ_1/2-X⁴Φ_3/2 and ⁴Δ_3/2-X⁴Φ_5/2 subbands. The effective equilibrium molecular constants for the [37.8]⁴Φ_3/2 and [37.8]⁴Φ_3/2 upper states were determined. In addition, lifetime measurements were carried out for all of the observed bands under collision-free conditions. On the basis of the spectroscopic constants and lifetime measurements, the electronic transitions involved in the observed high-lying electronic states are discussed.     

What is measured in a time-resolved stimulated Raman experiment?

We have performed four-beam time-resolved stimulated Raman measurements on liquid CS₂. To interpret our results we have applied the response formalism for the third-order polarization to such an experiment. It turns out that the measured quantity is proportional to (a convolution of) Abs[χ⁽³⁾(-ω_s, ω_s, ω_l, -ω_l)]. As a consequence in this four-beam e xperiment one picks up electronic contributions in contrast to a two-beam experiment where Im[χ⁽³⁾] is observed.     

The four quasi-particle 178Hf isomeric state,its excitation energy and multipolarities of deexciting transitions

The decay properties of the 31 y ¹⁷⁸Hf isomeric state have been investigated by means of a Ge(Li)-NaI(Tl) Compton suppression device and a Si(Li) detector, as well as with Ge(Li) and Ge(Li), intrinsic Ge and Si(Li) coincidence arrangements. From the E3 character of the unobserved isomeric transition (11.7 ≦ E_IT ≦ 16.7 keV), deduced from L-subshell and M/L ratios, I^π, K of the isomeric level was determined as 16⁺, 16. The {p[404] ↓ + p1514] ↑ + n[514] ↓ + n[624]↑}_16⁺ + four quasi-particle configuration was assigned to this level at 2447.5 ± 2.5 keV. As proposed earlier the isomeric E3 transition decays to the 13^? level of the band built upon the I^π = 8^? isomer. The |g_K?g_R| values derived from $\text{E}\text{2}\text{M}\text{1}$ ratios of interband transitions show that the 8^? isomer contains about 36 % of the p[404] ↓ + p[514] ↑ configuration and about 64 % of the n[624] ↑ + n[514] ↓ configuration.     

Ln(III)-cored complexes based on 2-thenoyltrifluoroacetone ligand for near infrared emission: Energy transfer pathway and transient absorption behavior

Lanthanide(III)-cored complexes based on 2-thenoyltrifluoroacetone (TTA) ligand for near infrared (NIR) emission have been developed to investigate the energy transfer pathway from the antenna ligand to the Ln³⁺ ion. Their photophysical studies indicate the sensitization of Ln³⁺ luminescence by energy transfer through the excited triplet state of β-diketone ligand. Nanosecond (ns) transient absorption behavior of Ln³⁺-[TTA]₃(terpy) complexes at room temperature is explored. The triplet-triplet absorption spectrum for Gd³⁺-[TTA]₃(terpy) is observed under degassed condition, whereas it is hardly observed in Er³⁺-[TTA]₃(terpy) complex. The sensitizing process in Er³⁺-[TTA]₃(terpy), through the triplet state of TTA ligand to Er³⁺ ion, is also independent on the presence of oxygen. It indicates that the energy transfer rate through the excited triplet state of β-diketone ligand to Er³⁺ ion occurs approximately faster than that of the oxygen quenching rate.     

Signature splitting in two quasiparticle rotational bands of <Superscript>180,182</Superscript>Ta

The signature splittings in K^π = 1 ⁺: 7 /2[404] _π?9 /2[624] _ν, K^π = 0^?: 9 /2[514] _π?9 /2[624] _ν bands of ¹⁸⁰Ta and K^π = 0^?: 7 /2[404] _π?7 /2[503] _ν, K^π = 1^?: 5 /2[402] _π?3 /2[512] _ν, K^π = 1⁺: 7 /2[404] _π?9 /2[624] _ν bands of ¹⁸²Ta are analysed within the framework of two-quasiparticle rotor model. The phase as well as magnitude of the experimentally observed signature splitting in K^π = 1⁺ band of ¹⁸⁰Ta, which could not be explained in earlier calculations, is successfully reproduced. The conflict regarding placement of a 12 ⁺ level in K^π = 1 ⁺: 7 /2 ⁺[404] _π?9 /2 ⁺[624] _ν ground-state rotational band of ¹⁸⁰Ta is resolved and tentative nature of K^π = 0^?: 7 /2[404] _π?7 /2[503] _ν, K^π = 1⁺: 7 /2[404] _π?9 /2[624] _ν bands observed in ¹⁸²Ta is confirmed. As a future prediction for experimentalists, these two-quasiparticle structures observed in ¹⁸⁰Ta and ¹⁸²Ta are extended to higher spins.     

High-Resolution Fourier Transform Spectroscopy of Three Near-Infrared Transitions of NiF

The emission spectrum of the NiF radical has been recorded by high-resolution Fourier transform spectroscopy in the region 6000-12 000 cm⁻¹. Numerous new near-infrared bands were observed. In this paper three electronic transitions are analyzed leading to the identification of two new electronic states: a [12.0]²Φ_7/2 state and a [11.1]²Π_3/2 state located, respectively, at 12 008.89 and 11 096.05 cm⁻¹ above the X²Π_3/2 ground state. These electronic states can be correlated to the [3d⁸(³F)4s]²F atomic term of Ni⁺ as predicted by Carette et al. [J. Mol. Spectrosc.161, 323-335 (1993)].     

Parelektrische Resonanz von Li+ in KCl

Parelectric resonance (PER) absorption spectra of Li⁺-centers in KCl crystals are measured at 35 and 9 GHz. Measurements for the microwave fieldE ₁ parallel and perpendicular to the static fieldE ₀ for three different orientations relative to the crystal axes can be explained by using the following offcenter tunneling model for the Li⁺-center: The dipole momentp=6.3±0.3 Debye is in [111] direction. Tunneling transitions are possible parallel to the [100] and [110] axis. The corresponding matrix elements are 11.3±0.5 and 3.2±0.5 GHz. The zero field splittings are 9.8±1.5; 22.6±1 and 35.4±3 GHz. Measurements under application of an uniaxial pressureP ₀ support this analysis.     

Structure of the highly deformed nucleus101Sr63 and evidence for identical K=3/2 bands

The low-energy level scheme of theN=63 nucleus¹⁰¹Sr has been obtained from a β-decay study of¹⁰¹Rb. The ν[532]5/2 and ν[411]3/2 orbitals are well established as the ground state and a band head at 271.2keV, respectively. The general properties of the level scheme indicate a quadrupole deformation ofβ ? 0.4, confirming the unique feature of saturation of deformation inN ≥ 60 Sr isotopes. The energies of theK=3/2 intraband transitions in the odd-neutron neighbours⁹⁹Sr₆₁ and¹⁰¹Sr₆₃ are very similar. More generally, the identical bands at low spin in^98–101Sr nuclei are correlated with the mass-independent moments of inertia in this region.     

The effect of spin states of iron[II] on the XPS of its mixed complexes

A series of mixed iron[II] phenanthroline complexes having analogous coordination spheres but containing the central iron atom in differing spin states (high-spin, ⁵T₂; low-spin, ¹A₁; and spin triplet, ³A₂) have been investigated by XPS. The data reflect the effects of the spin state of iron on the XPS pattern and on the electron binding energies. Fe[4,7-(C₂H₅OOC)₂phen] ₂(NCS)₂ is the first iron[II] complex in the ³A₂ spin state that has been studied by XPS.     

Synthesis and spectroscopic investigation of iron(III) complexes of N′-(thioaroyl)pyridine-2-carbohydrazides

A new series of iron(III) complexes [Fe(L¹)(HL¹)], [Fe(L¹)Cl]; [H₂L¹ = N′-(2-methoxythiobenzoyl)pyridine-2-carbohydrazide], [Fe(L²)(acac)], [Fe(HL²)₂Cl]; [H₂L² = N′-(4-methoxythiobenzoyl)pyridine-2-carbohydrazide] and [Fe(L³) (acac)]; [H₂L³ = N′-(2-hydroxythiobenzoyl)pyridine-2-carbohydrazide] were prepared by stirring/refluxing/mixing the respective ligand with FeCl₃/Fe(acac)₃ in chloroform/methanol. All the compounds were characterized by elemental analyses, magnetic susceptibility, IR, UV and Mössbauer spectral data. The complexes posses high/ low spin state and have tetrahedral/octahedral geometry.     

Backbendings of superdeformed bands in ~(36,40)Ar

Experimentally observed superdeformed(SD) rotational bands in ~(36)Ar and ~(40)Ar are studied by the cranked shell model(CSM) with the pairing correlations treated by a particle-number-conserving(PNC) method.This is the first time that PNC-CSM calculations have been performed on the light nuclear mass region around A=40.The experimental kinematic moments of inertia J~((1))versus rotational frequency are reproduced well. The backbending of the SD band at frequency around ω =1.5 Me V in ~(36)Ar is attributed to the sharp rise of the simultaneous alignments of the neutron and proton 1 d_(5/2)[202]5/2 pairs and 1 f_(7/2)[321]3/2 pairs, which is a consequence of the band crossing between the 1 d_(5/2)[202]5/2 and 1 f_(7/2)[321]3/2 configuration states. The gentle upbending at low frequency of the SD band in ~(40)Ar is mainly affected by the alignments of the neutron 1 f_(7/2)[321]3/2 pairs and proton 1 d_(5/2)[202]5/2 pairs.The PNC-CSM calculations show that besides the diagonal parts, the off-diagonal parts of the alignments play an important role in the rotational behavior of the SD bands.     

Elastic constants of Cr3Si

Elastic constants of Cr₃Si have been measured on single crystals oriented along [110] and [100] as a function of temperature between 4.2 and 300 K. Their magnitudes at 4.2 K are in unit of 10¹¹ Nm^-2C₄₄ = 1.32C' = (C₁₁?C₁₂)/2 = 1.58B = 1.99 There is no peculiar behaviour as a function of temperature.     

Longitudinal relaxation of Fe nuclei in Yb-doped YIG

Measurements of T₁ for ⁵⁷Fe nuclei in Yb-doped YIG are reported for the temperature range 0·7–140 K, with the magnetization along the [111], [100], [110], and [112] crystallographic directions respectively. The dependence of T₁ on Yb concentration and on the magnitude of the applied field was also studied. These results are interpreted in terms of the ‘slow relaxation theory’, and are correlated with the ferrimagnetic resonance work of Clarke, Tweedale, and Teale, whose data have been reanalyzed by us. Both sets of data can be represented fairly well by the theory, with a consistent set of relevant parameters. However, the tensor G which describes the splitting of the Yb ground-state doublet must be modified somewhat from that deduced by Clarke et al., the new principal values being G₁ = 29·0 cm⁻¹, G₂ = 20·4 cm⁻¹ and G₃ = 8·5 cm⁻¹ respectively. Below approximately 10 K, when the magnetization is in the [110] or [112] direction, the nuclear relaxation rate is higher than predicted. These anomalies correspond to those observed in ferrimagnetic resonance line width, which have been attributed to Yb ions on the octahedral lattice sites normally occupied by iron. Anomalously large values of T⁻¹₁ are also observed below approximately 4 K in the [111] and [100] directions, and these remain to be accounted for.     

Chemical tuning of high-spin complexes based on 3- and 4-hydroxy-pentadentate-Fe (III) complex-units investigated by Mössbauer spectroscopy

The pentadentate ligands 3-OH-⁵L?=?[N,N′-Bis(1,3-dihydroxy-2-benzylidene)-1,7-diamino-4-azaheptane] and 4-OH-⁵L?=?[N,N′-Bis(1,4-dihydroxy-2-benzylidene)-1,7-diamino-4-azaheptane] has been prepared by a Schiff base condensation between 1,7-diamino-4-azaheptane and the dihydroxybenzaldehyde. Complexation with Fe(III) yields high-spin (S?=?5/2) complexes of [Fe^III(3-OH-⁵L)Cl] and [Fe^III(4-OH-⁵L)Cl]. These precursors were combined with [M(CN) _x ] ^y? (M?=?W(IV), Mo(IV), Ru(II), Co(III)) and heptanuclear and nonanuclear clusters of [M{(CN-Fe^III(3-OH-⁵L)} _x ]Cl _y and [M{(CN-Fe^III(4-OH-⁵L)} _x ]Cl _y resulted. Such starshaped hepta- and nonanuclear compounds are high-spin systems at room temperature. On cooling to 10 K some of the iron(III) centers switch to a second high-spin state as proven by Mössbauer spectra, i.e. multiple electronic transitions. Parts of the compounds perform a high-spin to high-spin transition.     

Coherence effects in low energy Na*(3p)+Na+ scattering: Experiment and semiclassical calculations

Pronounced polarization effects have been observed in inelastic collisions of laser state-prepared Na^*(3p,M _L) with Na⁺ leading to Na^*(3d) for the energy rangeE _CM=20–45 eV. Using linearly polarized light the dependence of the inelastic process on the alignment of the electronic charge cloud of the Na^*(3p) prior to the collision has been measured. In studies with left and right hand circularly polarized light the angular momentum transferred in the collision process has been determined. The results are compared with similar data for the 3p→3s deexitation process studied previously [6]. The density matrix of the Na^*(3p) state has been evaluated with respect to the collisional excitation to Na^*(3d). Semiclassical calculations based on the coupled channel impact parameter approximation using pseudopotentials [7] and nonadiabatic rotational coupling elements for the Na ₂ ^* system [12] have been performed. The agreement with the experimental results is good, in particular for the higher collision energies.     

Hole concentration dependence of Mn eg orbital state in bilayer manganites studied by magnetic Compton profile measurement

Magnetic Compton profiles (MCP) have been measured in the [100], [110] and [001] directions on the single crystals of La_2−2xSr_1+2xMn₂O₇ (x=0.30, 0.35 and 0.42) at 10 K. The occupation numbers in t_2g and two e_g type orbitals (x²−y² and 3z²−r²) of Mn-3d state are evaluated from the line-shape analysis of MCP's in the [001] direction by using theoretical profiles derived from the ab initio calculations for (MnO₆)⁸⁻cluster. It has been found that the e_g state is dominated by the x²−y² type orbital at every hole concentration, x, and the 3z²−r² type orbital population decreases with increasing x. From the result, the connections of e_g orbital state with the electron correlation effect, exchange interactions, lattice distortion and electronic inhomogeneity are discussed.     

Effects of electron correlation and spin-orbit coupling on the electronic and magnetic properties of TbCu3Mn4O12

Electronic and magnetic properties of the three magnetic-sublattice double perovskite TbCu₃Mn₄O₁₂ (TCMO) are investigated by performing first-principles density-functional theory calculations. Our electronic structure calculations show that TCMO is half-metallic and its half-metallicity can only be correctly described when the electron correlation on Tb³⁺ 4f⁸ electrons are considered. The energies of different magnetic configurations among the three magnetic sublattices are also calculated, revealing that the magnetic configuration with Mn and Cu spins in the antiparallel arrangement and with the Tb magnetic moments ferromagnetically/antiferromagnetically (FM/AFM) coupled to Cu/Mn spins (that is Tb^↓Cu₃^↓Mn₄^↑O₁₂) is the lowest energetic magnetic state, which is consistent with recent experimental results. The magnetic anisotropy is further calculated for the [1 1 1], [1 1 0], and [0 0 1] spin quantization directions. It is found that the [1 1 1]-direction is more stable than the [1 1 0]- and [0 0 1]-directions by 123 and 135 meV per formula unit, respectively, indicating a significant magnetic anisotropy. Our detailed projected partial density of states analysis finally shows that Cu and Mn are antiferromagnetically coupled by superexchange interaction and Tb is expected to interact FM with A-site Cu and AFM with B-site Mn sublattices by way of 4f-2p-3d.     

Elastic constants of solid krypton at T = 77 K determined by inelastic neutron scattering

Long-wavelength acoustic phonons have been studied for each of the [ζ00]T, [ζ00]L, [ζζ0]L and [ζζ0]T₁ branches in solid Kr at T = 77 K by means of inelastic neutron scattering utilizing ‘cold neutrons’ as they are available in the long-wave length tail of the pile spectrum. The raw data have been corrected for resolution effects taking into account the curvature of the dispersion surface and variation of mode eigenvectors. It has turned out, that this yields appreciable shifts of the raw data. The results of our experiment give c₁₁ = 4·25 ± 0·10, c₄₄ = 2·04 ± 0·03, c₁₂ = 2·82 ± 0·12 and a value for B = (c₁₁ + 2c₁₂)/3 = 3·30 ± 0·09 × 10¹⁰ dyne/cm². Available thermodynamic data for Kr gives a derived value for B^ad = 2·58 ± 0·06 × 10¹⁰ dyne/cm² indicating a large difference between zero sound and first sound in solid Kr at high temperatures.