Crystal-field splitting of Pr<Superscript>3+</Superscript> ion multiplets in YPO<Subscript>4</Subscript> with allowance for interconfigurational interaction

The crystal-field splitting of the Pr³⁺ ion multiplets is analyzed with regard to the influence of excited opposite-parity configurations 4f ^{(N − 1)}5d and a configuration with charge transfer. Such an approach makes it possible to (i) refine the characterization of the Stark structure of multiplets by 39% compared with the approximation of a weak configurational interaction and (ii) determine the covalence parameters and the parameters of an odd-symmetry crystal field from experimental data for the Stark structure. The covalence parameters thus determined coincide in order of magnitude with the respective parameters calculated for other ligands using microscopic models.     

Spectra energy levels and symmetry assignments of Sm3+ doped in YAl3(BO3)4 single crystal

Single crystals of YAl₃(BO₃)₄ doped with 5% Sm³⁺ were grown by spontaneous nucleation from K₂Mo₃O₁₀ and B₂O₃ flux. Photoluminescence spectra at room and low temperatures were measured. Four emission transitions have been observed from the ⁴G_5/2 excited state to the lower lying states ⁶H_5/2, ⁶H_7/2, ⁶H_9/2 and ⁶H_11/2 upon exciting the sample with 400 nm wavelength. Polarized absorption spectra in UV, visible and NIR regions were recorded for two light polarizations (π and σ) relative to the C₃ crystal axis.Energy levels scheme of the doping ion has been compiled after a careful analysis of the spectra by reproducing the observed transitions by means of theoretical calculations based on a Hamiltonian including the free-ion and the crystal-field (CF) terms. Free-ion and crystal-field analyses are performed based on a D₃ point-group symmetry Hamiltonian. A best fit between theoretical and experimental energy levels is obtained with a root-mean-square (rms) deviation of 16 cm^?1. The general trend of the crystal-field parameters of rare earth ions in YAB host is confirmed. The calculated N_V crystal-field strength parameter presents a linear variation with the rare earth ionic radii and with the 4fⁿ electron number.     

Comparative electronic structure of a lanthanide and actinide diatomic oxide: Nd versus U

Using a modified version of the Alchemy electronic structure code and relativistic pseudopotentials, the electronic structure of the ground and low lying excited states of UO, NdO, and NdO⁺ have been calculated at the Hartree—Fock (HF) and multiconfiguration self-consistent field (MCSCF) levels of theory. Including results from an earlier study of UO⁺ this provides the information for a comparative analysis of a lanthanide and an actinide diatomic oxide. UO and NdO are both described formally as M⁺²O^?2 and the cations as M⁺³O^?2, but the HF and MCSCF calculations show that these systems are considerably less ionic due to large charge back-transfer in the π orbitals. The electronic states putatively arise from the ligand field (oxygen anion) perturbed f⁴, sf³, df³, sdf², or s²f² states of M⁺² and f³, sf² or df² states of M⁺³. Molecular orbital results show a substantial stabilization of the sf³ or s²f² configurations relative to the f⁴ or df³ configurations that are the even or odd parity ground states in the M⁺² free ion. The compact f and d orbitals are more destabilized by the anion field than the diffuse s orbital. The ground states of the neutral species are dominated by orbitals arising from the M⁺²sf³ term, and all the potential energy curves arising from this configuration are similar, which allows an estimate of the vibrational frequencies for UO and NdO of 862 cm^?1 and 836 cm^?1, respectively. For NdO⁺ and UO⁺ the excitation energies for the Ω states were calculated with a valence configuration interaction method using ab initio effective spin—orbit operators to couple the molecular orbital configurations. The results for NdO⁺ are very comparable with the results for UO⁺, and show the vibrational and electronic states to be interleaved.     

Spectroscopic investigations and configuration-interaction-assisted crystal field analysis of Pr in YPO4 single crystal

An optical study of a Y_0.99Pr_0.01PO₄ single crystal is presented. Measurements of optical absorption, excitation, and emission by selective excitation into ¹D₂, ³P₀ and ³P₁, at different temperatures between 20 and 295 K, are described. A detailed account of the line assignments is given for absorption in the 4300-23 000 cm⁻¹ spectral range, and for emission in the 6400-23 000 cm⁻¹ range. The lifetimes of the emitting levels are determined. Vibronic sidebands accompanying absorption, emission and excitation spectra are reported. The decay processes of the ³P₁, ³P₀ and ¹D₂ levels are discussed. The aim of this study is a test of the configuration-interaction-assisted crystal field analysis as well as the accurate experimental determination of the energy level scheme. It was reported previously that the introduction of configuration interaction between the ground 4f² configuration with the excited 4f6p configuration always resulted in a decrease (≈50-60%) in the standard deviations between the observed and calculated energy levels. In the present work the 4f5d configuration is included as well. The crystal field is analysed in the theoretical D_2d site symmetry with and without configuration interaction. The results with 4f², 4f²+4f5d, 4f²+4f6p and 4f²+4f5d+4f6p are given. The calculation on the basis of the 315 (4f²+4f5d+4f6p) levels gives the best overall standard deviation lowering it by 75% with regard to the calculation on the 91 4f² levels only.     

Cl2 adsorption on MgO(001) surface supported sodium monolayers: a density functional theory study

The adsorption of Cl₂ Na monolayers supported on the MgO(001) surface has been studied by the density functional method using cluster models embedded in a large array of point charges (PCs). The value of PCs was determined by charge self-consistent technique. The results indicate that Na-promoted MgO(001) surface is an efficient catalyst toward Cl₂ adsorptive decomposition. Besides, it was found that the role of the MgO(001) surface is not passive, which is different from CO adsorption on MgO(001) surface supported Na metal monolayers. The analysis of band and projected density of states indicates that the electron transfer from the surface Mg 3s valence orbital and Na 3s valence orbital to the anti-bonding σ^∗ orbital of Cl₂ is the source of the Cl₂ bond weakening. This is also different from the CO adsorption on MgO(001) surface supported Na metal monolayers, where only the electrons from the Na valence orbital are transferred to the anti-bonding π^∗ orbital of adsorbed CO. Our study suggests that the essence of catalysis is different for CO and Cl₂ adsorption on Na metal monolayers supported an MgO(001) surface.     

Action du champ cristallin sur l'ion Er3+ dans l'oxysulfure de terre rare Er2O2S

The Er³⁺ electronic ion structure, in its 4f¹¹ configuration, has been determined by the optical absorption spectrum of Er₂O₂S. By the use of the Slater parameters F₂ = 424,4, F₄ = 66,1, F₆ = 6,87 cm^?1 and the Spin-orbit parameter ζ = 2367 cm^?1, the experimental ‘free-ion’ energy levels have been fitted with a r.m.s. deviation of 78 cm^?1. In intermediate coupling, the crystal field parameters V₂⁰ = 90, V₄⁰ = 175, V₄³ = 2365, V₆⁰ = 0,5, V₆³ = 205 and V₆⁶ = 180 cm^?1 give the best fit with experimental data. For 56 Stark levels involved the calculation predicts the splittings with a r.m.s. deviation of 12 cm^?1. The magnetic susceptibility has been calculated and is in satisfactory agreement with experimental powder measurements.     

Isotopic shifts and the hyperfine structure of the samarium spectral lines at 672 and 686 nm

Spectra of saturated absorption of Sm atomic vapor from the ground state ⁷ F ₀ and the first even metastable level ⁷ F ₁, ε′=292.58 cm^?1 of the 4f ⁶6s ² configuration to the odd level 4_f ⁶(⁷ F)6s6p(³ P ^o)⁹ F ₁ ^o , ε,=14863.85 cm^?1 were recorded. The lines of the isotopic series were identified, and the hyperfine structure of lines in the spectra of isotopes with a nonzero nuclear spin was determined. The relative isotopic shifts and the hyperfine splitting of the even level 4f ⁶6s ²(⁷ F ₁) were determined.     

The electronic structures of the core and valence ion states of metal oxides

SCF-Xα SW MO calculations on metal core ion hole states and X-ray emission (XES) and X-ray photoelectron (XPS) transition states of the non- transition metal oxidic clusters MgO₆^10?, AlO₄^5? and SiO₄^4? show relative valence orbital energies to be virtually unaffected by the creation of valence orbital or metal core orbital holes. Accordingly, valence orbital energies derived from XPS and XES are directly comparable and may be correlated to generate empirical MO diagrams. In addition, charge relaxation about the metal core hole is small and valence orbital compositions are little changed in the core hole state. On the other hand, for the transition metal oxidic clusters FeO₆^10?, CrO₆^9? and TiO₆^8? relative valence orbital energies are sharply changed by a metal core orbital or crystal field orbital hole, the energy lowering of an orbital increasing with its degree of metal character. Consequently O 2p nonbonding → M 3d-O 2p antibonding (crystal field) energies are reduced, while M 3d bonding → O 2p nonbonding and M 3d-O 2p antibonding → M 4s,p-O 2p antibonding (conduction band) energies increase. Charge relaxation about the core hole is virtually complete in the transition metal oxides and substantial changes are observed in the composition of those valence orbitals with appreciable M 3d character. This change in composition is greater for e _g than for t_2g orbitals and increases as the separation of the e_g crystal field (CF) orbitals and the O 2p nonbonding orbital set decreases. Based on the hole state MO diagrams the higher energy XPS satellite in TiO₂ (at about 13 eV) is assigned to a valence → conduction band transition. The UV PES satellites at 8.2 eV in Cr₂O₃ and 9.3 eV in FeO are tentatively assigned to similar transitions to conduction band orbitals, although the closeness in energy of the crystal field and O 2p nonbonding orbitals in the valence orbital hole state prevents a definite assignment on energy criteria alone. However the calculations do clearly show that charge transfer transitions of the e_g bonding → e_g crystal field orbital type would generally occur at lower energy than is consistent with observed satellite structure.A core electron hole has little effect upon relative orbital energies and is only slightly neutralized by valence electron redistribution for MgO and SiO₂. For the transition metal oxides a core hole lowers the relative energies of M3d containing orbitals by large amounts, reducing O → M charge transfer and increasing M 3d crystal field → conduction band energies. Large and sometimes overcomplete neutralization of the core hole is observed, increasing from CrO₆^9? to FeO₆^10? to TiO₆^8?. as the O → M charge transfer energy declines.High energy XPS satellites in TiO₂ may be assigned to O 2p nonbonding → conduction band transitions while lower energy UV PES satellites in FeO and Cr₂O₃ arise from crystal field or O 2p nonbonding → conduction band excitations. Our “shake-up” assignment for FeO₆^10?, CrO₆^9? and TiO₆^8? are less than definitive because no procedure has yet been developed to calculate “shake-up” intensities resulting from transitions of the type described. However the results do allow a critical evaluation of earlier qualitative predictions of core and valence hole effects. First, we find that the comparison of hole or valence state ionic systems with equilibrium distance systems of higher nuclear and/or cation charge (e.g. the comparison of the FeO₆^10? Fe 2p core hole state to Co₃O₄) is dangerous. For example, larger MO distances in the ion states substantially reduce crystal field splittings. Second, core and CF orbital holes sharply reduce O → M charge transfer energies, giving 2e_g → 3e_g energy separations which are generally too small to match observed satellite energies. Third, highest occupied CF-conduction band energies are only about 4–5 eV in the ground states, but increase to about 7–11 eV in the core and valence hole states of the transition metal oxides studied. The energetic arguments presented thus support the idea of CF and/or O 2p nonbonding → conduction band excitations as assignments for “shake-up” satellites, at least in oxides of metals near the beginning of the transition series.     

Electronic structure and properties of strontium ferrite Sr3Fe2O6

The electronic structure of strontium ferrite Sr₃Fe₂O₆ was calculated using the tight-binding linear muffin-tin orbital method (TB LMTO) in the local spin density approximation of density functional theory with Coulomb correlations correction (LSDA+U). The semiconducting character of the spectrum with charge transfer energy gap of 1.82 eV was obtained in reasonably good agreement with experimental data. The iron ions are found to be in the high spin state. The calculated value of the local spin magnetic moment of Fe³⁺ ion is 3.94 μ_B which is not typical for trivalent iron ion in the high spin state. It is shown that the strong hybridization between Fe3d and O2p orbitals favors the d⁶ L configuration of Fe³⁺ ion, where L is a hole in the oxygen p shell. The mechanism of oxygen transport in ferrite is discussed basing on the total energy calculations of the different spatial configurations of oxygen vacancies.     

High resolution measurements of the hyperfine structure in 10 levels of Tm I

High resolution laser spectroscopy has been performed on an atomic beam of thulium. Accurate values for the magnetic dipole coupling constants of 9 excited levels belonging to the 4f¹³ 6s6p and 4f¹²5d6s² configurations and of the metastable level at 8771 cm^?1 belonging to the 4f¹³6s² ground state configuration have been obtained.     

Single-electron charge transfer and excitations at collisions between Bi<Superscript>4+</Superscript> ions in the kiloelectronvolt energy range

Pioneering theoretical data for single-electron charge transfer and excitations due to collisions between Bi⁴⁺ ions in the ground (6s) and metastable (6p) states are gained in the collision energy interval 5–75 keV in the center-of-mass frame. The cross sections of the processes are calculated in terms of the close-coupling method in the basis of two-electron quasi-molecular states for the Coulomb trajectory of nuclei. It is found that single-electron capture into the singlet 6s ² states of Bi³⁺ ions makes a major contribution to the charge transfer total cross section for Bi⁴⁺(6s) + Bi⁴⁺(6s) collisions (reaction 1), whereas single-electron capture into the singlet 6s6p states is the basic contributor to the total cross section in Bi⁴⁺(6s) + Bi⁴⁺(6p) collisions (reaction 2). In the collision energy interval mentioned above, the collision cross sections vary between 1.2 × 10^?17 and 1.9 × 10^?17 cm² for reaction 1 and between 3.8 × 10^?17 and 5.3 × 10^?17 cm² for reaction 2. In reaction 1, the 6s → 6p excitation cross sections vary from 0.6 × 10^?16 to 0.8 × 10^?16 cm² for the singlet channel and from 2.2 × 10^?16 to 2.8 × 10^?16 cm² for the triplet channel. The calculation results are compared with the data obtained in experiments with crossed ion beams of kiloelectronvolt energy. The fraction of metastable ions in the beams is estimated by comparing the experimental data with the weighted average theoretical results for the cross sections of reactions 1 and 2. From the data for the charge transfer cross sections, one can estimate particle losses in relativistic beams due to a change in the charge state of the ions colliding with each other in the beam because of betatron oscillations.     

Absorptionsspektrum des Ce3+-Ions und Kristallfeld im La(Ce)Cl

The absorption spectrum of single crystals of La_(1?x)Ce _x Cl₃(x=0,05 ... 0,005) has been observed at low temperatures in the region of the 4f→4f infrared transitions. Values for the crystal-field parameters V ₂ ⁰ , V ₄ ⁰ , V ₆ ⁰ , V ₆ ⁶ and for the spin-orbit coupling constant of the ion in the crystalline environment are determined by fitting the observed splittings of the multiplet-components\({}^2F_{\tfrac{5}{2}} \) and\({}^2F_{\tfrac{7}{2}} \) in the crystal-field. The parameters are found to be consistent with values extrapolated from rare earth-ions with neighbouring atomic numbers in the same host-lattice. The only exception is the parameter V ₆ ⁶ , which is found to be smaller in La(Ce)Cl₃ than in other rare-earth-trichlorides (V ₆ ⁶ /V ₆ ⁰ =?6,23 in La(Ce)Cl₃, V ₆ ⁶ /V ₆ ⁰ ≈?10 in other trichlorides). The correct relation V ₆ ⁶ /V ₆ ⁰ in La(Ce)Cl₃ is obtained by fitting the parameters to the observed crystal-field-splitting of the\({}^2F_{\tfrac{5}{2}} \) — component and to the observed Zeeman-splitting-factors taken from the literature. The discrepancies between the two fitting procedures are explained by an effect of nonlinear shielding of the crystal-field.     

An E.S.R. study of electron irradiated K3IrCl6 in a NaCl host lattice

Electron irradiation of the diamagnetic [Ir^IIICl₆]^3- ion in a NaCl host lattice produces two paramagnetic species. ESR studies indicate that these slightly different species can be assigned to a [Ir^IICl₆]^4- complex, with 5d ⁷ low spin configuration, arising from the capture of an electron in a d_z ² orbital. The almost zero value for the quadrupolar interaction and the negative value for the core polarization field per unpaired spin are discussed in terms of a ligand field theory and the group overlap integral for the A _1g molecular orbital is calculated from the experimental data.     

Molecular engineering of the electronic,structural, and electrochemical properties of nanostructured 1-methyl-4-phenyl 1,2,4 triazolium-based [PhMTZ][X<Subscript>1–10</Subscript>] ionic liquids through anionic changing

In the present work, molecular engineering of the physicochemical characteristics of ion pairing in 1-methyl-4-phenyl 1,2,4 triazolium-based ionic liquids [PhMTZ][X] (X_1–10 = CH₃CO₂ ^?, Cl^?, NO₃ ^?, CF₃CO₂ ^?, BF₄ ^?, ClO₄ ^?, N(CN)₂ ^?, PF₆ ^?, NTf₂ ^?, and C(CN)₃ ^?) are explored using at M06-2X/6–311++G(d,p) level. The binding Gibbs free energy of ion pairs are reevaluated using ab initio MP2 method and dispersion corrected M06-2X-D3, B2PLYP, B2PLYP-D, and mPW2PLYP-D functionals. Comparison of Gibbs free bottom electrodes (BEs) calculated by B2PLYP and B2PLYP-D functionals reveals that the contribution of dispersion energy to the total BEs vary from 9% for X1 to 17% for X = 10. Besides, the range of the dispersion contribution estimated by M06-2X-D3 functional is found to be 0.6% for X₂ to 5% for X₃. The Gibbs free BEs in solvent media, Gibbs free energy and enthalpy of formation, electrochemical windows, anodic and cathodic stability, volumetric and electron density properties, charge transfer values, and electrostatic maps are evaluated.     

Absorption Spectra of Lanthanide Complexes in Solution

Abstract

The 4f electrons of lanthanides yield three types of transitions: (i) Internal 4f-4f transitions which give rise to sharp, narrow bands of comparatively weak intensities which are Laporte forbidden. (ii) Allowed 4fⁿ?4f^n-1 (n – l)d, which are relatively broad and intense. (iii) Broad and often intense 4fⁿ?λ^?1 fⁿ⁺¹ electron transfer bands generally occurring in the ultraviolet region (λ^? represents a hole in the orbital concentratedmainly on the ligands).     

Spectroscopic and quantum-chemical investigations of chloro-bis-bipyridyl complexes of ruthenium(II) with 4-substituted pyridine ligands

The luminescence spectra of cis-[Ru(bpy)₂(L)Cl]⁺ (bpy is 2,2′-bipyridyl; L is pyrazine, pyridine, 4-amino-pyridine, 4-picolin, isonicotinamide, 4-cyanopyridine, or 4,4′bipyridyl) complexes are studied in alcoholic (4: 1 EtOH-MeOH) solutions at 77 K. A linear correlation is found between the energy of the lowest electronically excited metal-to-ligand charge transfer (³MLCT) state d _π(Ru) → π* (bpy) and the parameter pK _a of the free 4-substituted pyridines and pyrazine used as ligands L. The [B3LYP/6-31G + LanL2DZ(Ru)] hybrid method of the density functional theory is used to optimize the geometry of complexes and calculate their electronic structure and the charge distribution on the atoms of the nearest environment of the ruthenium ion. It is shown that there exists a linear unambiguous correlation between the negative charge on the nitrogen atom (qN ^L) of ligands L coordinated in the complex and the parameters pK _a of free ligands. The calculated energies of ³MLCT excited states almost linearly (correlation coefficient 0.958) depend on the charge qN ^L, which completely agrees with experimental data.     

X-ray excited optical luminescence spectrum of Pr-doped YPO4

The X-ray excited optical luminescence spectrum of Pr³⁺ in YPO₄ was investigated. In addition to the sharp line f-f transitions involving the energy levels of the 4f² configuration of Pr³⁺ ion, the spectrum contains some broad groups of fluorescence lines in the ultraviolet and blue region. These groups of fluorescence are attributed to transitions from the lowest 4f^I5d state at 43050 cm^-1 to the 4f² levels of the Pr³⁺ion in YPO₄.     

The key Cl− ligand for metal‐to‐ligand charge transfer in mononuclear terpyridine ruthenium(II) and binuclear ruthenium(II) tetrapyridylpyrazine complexes

Electronic structures of binuclear ruthenium complexes [Ru₂(terpy)₂(tppz)]⁴⁺ ( 1A ) and [Ru₂Cl₂(L)₂(tppz)]²⁺ {L = bpy ( 2A ), phen ( 3A ), and dpphen ( 4A )} were studied by density functional theory calculations. Abbreviations of the ligands (Ls) are bpy = 2,2′‐bipyridine, phen = 1,10‐phenanthroline, dpphen = 4,7‐diphenyl‐1,10‐phenanthroline, terpy = 2,2′:6′,2″‐terpyridine, and tppz = tetrakis(2‐pyridyl)pyrazine. Their mononuclear reference complexes [Ru(terpy)₂]²⁺ ( 1B ) and [RuClL(terpy)]⁺ {L = bpy ( 2B ), phen ( 3B ), and dpphen ( 4B )} were also examined. Geometries of these mononuclear and binuclear Ru(II) complexes were fully optimized. Their geometric parameters are in good agreement with the experimental data. The binuclear complexes were characterized by electrospray ionization mass spectrometry, UV–Vis spectroscopy, and cyclic voltammograms. Hexafluorophosphate salts of binuclear ruthenium complexes of 3A and 4A were newly prepared. The crystal structure of binuclear complex 1A (PF₆)₄ was also determined. Orbital interactions were analyzed to characterize the metal‐to‐ligand charge‐transfer (MLCT) states in these complexes. The Cl^? ligand works to raise the orbital energy of the metal lone pair, which leads to the low MLCT state. Copyright © 2011 John Wiley & Sons, Ltd.     

Measurement of hyperfine structure and isotope shifts in the 580.56nm line of 142－145,146,148,150Nd+

Isotope shifts and hyperfine spectrum of singly ionized neodymium ion was measured by collinear fast-ion-beam laser spectroscopy. The hyperfine A constants and B constants are obtained for the (23230)9/2^0 level and 4f^45d ^6K9/2 level, respectively. The optical isotope shifts between seven isotopes in the 580.56 nm of^142-145,146,148,150Nd^ line are determined. The configuration admixtures for (23230)9/2^0 level were quantitatively analysed to be 4f^46p, 4f^35d^2, and 4f^35d6p with mixing coefficients of 67%, 5%, and 28%, respectively.     

铈激活磷光体的发光特性

Ce3+的发光属于f-d跃迁,它的荧光寿命非常短,发射光谱呈现带状,并随着基质的不同,发射峰位置发生显著的变化,能从紫外一直到可见区.Ce3+发射峰位置的变化与基质中直接配位的阴离子、阳离子以及阴离予基团等的变化有关,也受晶场劈裂、Stokes位移的影响.Ce3+发射峰位置的变化与化台物的共价程度有关,并得到一些规律性的结果,这将为材料设讨提供依据.文中对一些典型的Ce3+的能量传递和敏化作用作了介绍.