Key Role of Deep Orbitals in the dx2-y2-d3z2-r2 Gap in Tetragonal Complexes and 10Dq.

Using first-principles calculations, we show that the origin of the intrinsic a1g(∼3z2 - r2)-b1g(∼x2 - y2) splitting, Δint, in tetragonal transition-metal complexes and the variations of the cubic field splitting, 10Dq, with the metal-ligand distance, R, are much more subtle than commonly thought. As a main novelty, the key role played by covalent bonding with deep valence ligand levels and thus the inadequacy of too simple models often used for the present goal is stressed. Taking as a guide the isolated D4h CuF64- complex, it is proved that Δint essentially arises from bonding with deep 2s(F) orbitals despite them lying ∼23 eV below 2p(F) orbitals. This conclusion, although surprising, is also supported by results on octahedral fluoride complexes where the contribution to 10Dq splitting from bonding with 2s(F) orbitals is behind its strong R dependence, stressing that explanations based on the crystal-field approach are simply meaningless.

Local structure and excitations in systems with CuF64- units: lack of Jahn-Teller effect in the low symmetry compound Na2CuF4.

This work attempts to unveil the similarities and differences between Jahn-Teller (JT) and non-JT systems involving CuF64- units. For achieving this goal, we firstly explore Na2CuF4 and NaF:Cu2+ systems through first principles calculations and pay particular attention to the links between JT and non-JT systems looking at the electronic density of the hole. The results on Na2CuF4 in the monoclinic P21/c space group and also in the parent Pbam structure reveal that the local geometry can be understood as an initial tetragonally compressed CuF64- unit, followed by an additional orthorhombic instability that excludes the JT effect as the origin. Although the present results on NaF:Cu2+ underpin an elongated equilibrium geometry such as that measured for Cu2+ ions in the cubic perovskite KZnF3, the force constant for NaF:Cu2+ is half that for KZnF3:Cu2+. This crucial fact is direct proof of the elastic decoupling of CuF64- from the NaF lattice leading to a JT energy, EJT, which is twice that found for KZnF3:Cu2+. However, both systems have practically the same linear electron-vibration coupling constant, V1e, a relevant fact whose origin is discussed. The final aim of this work concerns the influence of tetragonal and orthorhombic distortions as well as the internal electric field on the A1g-B1g energy gap, Δ, of a variety of systems with CuF64- complexes. Interestingly, it is shown that compounds with orthorhombic instability and an internal electric field can have a Δ value comparable to the JT system NaF:Cu2+. Accordingly, explanations for optical spectra of transition metal compounds based on simple parameterized models can be meaningless. The present study shows that properties displayed by d9 compounds in low symmetry lattices can hardly stem from a static JT effect.

Explaining the optical spectrum of CrF2 and CuF2 model materials: role of the tetragonal to monoclinic instability.

The properties of MF2 (M = Cr, Cu) model compounds are usually interpreted assuming a Jahn-Teller effect leading to elongated MF64- units. By means of the analysis of experimental data and first-principles calculations on both the monoclinic P21/c structure and the parent rutile structure (tetragonal P42/mnm space group), we prove that such an assumption is not correct. It is shown that in MF2 compounds, the MF64- complexes are actually compressed in the parent phase but along a different direction, a situation that is however hidden by an additional orthorhombic instability due to a negative force constant of b2g and b3g modes of the cell. This distortion plays a key role in understanding the high experimental value of the lowest d-d transition energy, E1 = 1.23 and 0.93 eV for CrF2 and CuF2, respectively, when compared to the value E1 = 0.40 eV derived for the Jahn-Teller system of KZnF3:Cu2+. Aside from reproducing reasonably the experimental values of spin allowed d-d transitions of both compounds, our first-principles calculations show the existence of an accidental degeneracy involving the yz and xy levels in the final P21/c structure. Moreover, the internal electric field of CrF2 and CuF2 is found to be much less anisotropic than in layered compounds like K2CuF4 and thus it has little influence on the d-d transition energy. The influence of the (3z2 - r2) - (x2 - y2) hybridization, caused by the orthorhombic distortion, on the electronic density and the magnetic coupling between layers is also briefly discussed. The present results stress that the interpretation of experimental data using simple parameterized models can lead to wrong conclusions.

Quantifying local and cooperative components in the ferroelectric distortion of BaTiO(3): learning from the off-center motion in the MnCl(6)(5-) complex formed in KCl:Mn(+).

The delicate balance between cooperative and local contributions in the ferroelectric distortions of BaTiO3 is explored by means of ab initio calculations. As a salient feature, it is found that a single Ti(4+) ion in BaTiO3 is not allowed to move off-center at ambient pressure, while this is no longer true if the lattice is expanded by only ∼5%, stressing the high sensitivity of the local contribution to chemical and hydrostatic pressures. In order to further understand the effect of local contributions on the phase transition mechanism of ferroelectrics, we have investigated the surprising C3v → C4v → Oh local transformations occurring in the 10-50 K temperature range for the MnCl6(5-) complex formed in KCl:Mn(+) that mimic the behavior of BaTiO3. From Boltzmann analysis of the vibronic levels derived from ab initio calculations and considering decoherence introduced by random strains, the present calculations reproduce the experimental phase sequence and transition temperatures. Furthermore, our calculations show that the off-center instability in KCl:Mn(+) would be suppressed by reducing by only 1% the lattice parameter, a situation that then becomes comparable to that found for BaTiO3 at ambient pressure. The present results thus stress the deep link between the structural phase transitions of ferroelectric materials and local phase transitions displayed by transition-metal impurities in insulators.

Sharp lines due to Cr³âº and Mn²âº impurities in insulators: going beyond the usual Tanabe-Sugano approach.

This work is aimed at understanding the different behavior of optical sharp lines (corresponding to 10Dq-independent transitions) of Mn(2+) and Cr(3+) in normal and inverted perovskites that cannot be explained within the usual Tanabe-Sugano approach. In particular, we want to clarify why on passing from KMgF3:M to LiBaF3:M (M = Mn(2+), Cr(3+)) the energy, E((6)A1 → (4)A1), for Mn(2+) decreases by Δ = 1100 cm(-1), while Δ < 100 cm(-1) for the energy E((2)E →( 4)A2) corresponding to Cr(3+). The origin of this surprising difference in these model systems is clarified by writing the transition energies of MF6 complexes through the ten Coulomb and exchange integrals consistent with the cubic symmetry and not considered in the usual Tanabe-Sugano approach. It is shown that E((6)A1 → (4)A1) depends on exchange integrals K(3z(2) - r(2), xy) and K(x(2) - y(2), xy), while E((2)E → (4)A2) depends on K(xz, yz) where the two involved electrons display a π character. These exchange integrals have been calculated just considering a MF6 unit subject to the internal electric field due to the rest of the lattice ions. In addition to a reasonably reproduction of the main trends observed experimentally for the model systems, the present calculations prove that the exchange integrals are not related in a simple way to the covalency of involved orbitals. Particular attention is also paid to explain why the transitions, which are 10Dq-independent are less sensitive to the host lattice change than those which do depend on 10Dq. The present work shows that K(xz, yz) for Cr(3+) is particularly insensitive to the host lattice change and thus sheds light on the origin of the near independence of E((2)E → (4)A2) along the series of oxides doped with such an impurity .

Transition metal complexes coupled to vacancies in oxides: origin of different properties of Cr3+ in MgO bounded to a <100> or <110> Mg2+ vacancy.

Despite the importance of vacancies over the properties of insulating oxides its influence on neighboring transition metal ions is far from being understood. This work is devoted to find the origin of various up to now unexplained properties of chromium bounded either to a <100> or a <110> Mg(2+) vacancy in MgO. In these model systems particular attention is paid to understand, by means of ab initio calculations, why the cubic field splitting parameter, 10Dq, is surprisingly 1600 cm(-1) higher for a <100> than for a <110> vacancy, a fact behind the suppression of the sharp (2)E → (4)A2 luminescence in the latter case. Our calculations, which reproduce the main experimental facts, prove that the average Cr(3+)-O(2-) distance is the same within 0.8% for both systems, and thus, the low 10Dq value for a <110> vacancy is shown to be due mainly to the electrostatic potential from the missing Mg(2+) ion, which increases the energy of antibonding t(2g) (∼xy, xz, yz) levels. By contrast, for a <100> Mg(2+) vacancy that potential provides a supplementary increase of the e(g) (∼x(2) - y(2), 3z(2 )- r(2)) level energy and thus of 10Dq. The existence of the (2)E → (4)A2 luminescence for Cr(3+)-doped MgO under perfect cubic symmetry or with a <100> vacancy is shown to be greatly helped by the internal electric field created by the rest of the lattice ions on the CrO6(9-) unit, whose importance is usually ignored. The present results underline the role of ab initio calculations for unveiling the subtle effects induced by a close vacancy on the properties of transition metal ions in oxides. At the same time they stress the failure of the empirical superposition model for deriving the equilibrium geometry of C4v and C2v centers in MgO:Cr(3+).

Origin of small barriers in Jahn-Teller systems: quantifying the role of 3d-4s hybridization in the model system NaCl:Ni+.

Despite its relevance, the microscopic origin of the energy barrier, B, between the compressed and elongated geometries of Jahn-Teller (JT) systems is not well understood yet because of a lack of quantitative data about its various contributions. Seeking to clear up this matter, we have carried out both periodic and cluster ab initio calculations on the model system NaCl:Ni(+). This system is particularly puzzling because, according to experimental data, its barrier is much smaller than that for other d(9) and d(7) ions in similar lattices. All calculations performed on the model system lead, in fact, to values |B| ≤ 160 cm(-1), which are certainly smaller than B = 500 cm(-1) derived for NaCl:M(2+) (M = Ag, Rh) or B = 1024 cm(-1) obtained for KCl:Ag(2+). As a salient feature, analysis of calculations carried out as a function of the Qθ (∼3z(2) - r(2)) coordinate unveils the microscopic origin of the barrier. It is quantitatively proven that the elongated geometry observed for NaCl:Ni(+) is due to the 3d-4s vibronic admixture, which is slightly larger than the anharmonicity in the eg JT mode that favors a compressed geometry. The existence of these two competing mechanisms explains the low value of B for the model system, contrary to cases where the complex formed by d(9) or d(7) ions is elastically decoupled from the host lattice. Although the magnitude of B for NaCl:Ni(+) is particularly small, the tunneling splitting, 3Γ, is estimated to be below 9 cm(-1), thus explaining why the coherence is easily destroyed by random strains and thus a static JT effect is observed experimentally. As a main conclusion, the barrier in JT systems cannot be understood neglecting the tiny changes of the electronic density involved in small distortions. The present calculations reasonably explain the experimental g tensor of NaCl:Ni(+), pointing out that the d-d transitions in NiCl6(5-) are much smaller than those for CuCl6(4-) and the optical electronegativity of Ni(+) is only around 1.

Cu2+ in layered compounds: origin of the compressed geometry in the model system K2ZnF4:Cu2+.

Many relevant properties (including superconductivity and colossal magnetoresistance) of layered materials containing Cu(2+), Ag(2+), or Mn(3+) ions are commonly related to the Jahn-Teller instability. Along this line, the properties of the CuF6(4-) complex in the K2ZnF4 layered perovskite have recently been analyzed using a parametrized Jahn-Teller model with an imposed strain [Reinen, D. Inorg. Chem.2012, 51, 4458]. Here, we present results of ab initio periodic supercell and cluster calculations on K2ZnF4:Cu(2+), showing unequivocally that the actual origin of the unusual compressed geometry of the CuF6(4-) complex along the crystal c axis in that tetragonal lattice is due to the presence of an electric field due to the crystal surrounding the impurity. Our calculations closely reproduce the experimental optical spectrum. The calculated values of the equilibrium equatorial and axial Cu(2+)-F(-) distances are, respectively, R(ax) = 193 pm and R(eq) = 204 pm, and so the calculated distortion R(ax) - R(eq) = 11 pm is three times smaller than the estimated through the parametrized Jahn-Teller model. As a salient feature, we find that if the CuF6(4-) complex would assume a perfect octahedral geometry (R(ax) = R(eq) = 203 pm) the antibonding a(1g)*(∼3z(2) - r(2)) orbital is placed above b(1g)*(∼x(2) - y(2)) with a transition energy E((2)A(1g) → (2)B(1g)) = 0.34 eV. This surprising fact stresses that about half the experimental value E((2)A(1g) → (2)B(1g)) = 0.70 eV is not due to the small shortening of the axial Cu(2+)-F(-) distance, but it comes from the electric field, E(R)(r), created by the rest of the lattice ions on the CuF6(4-) complex. This internal field, displaying tetragonal symmetry, is thus responsible for the compressed geometry in K2ZnF4:Cu(2+) and the lack of symmetry breaking behind the ligand relaxation. Moreover, we show that the electronic energy gain in this process comes from bonding orbitals and not from antibonding ones. The present results underline the key role played by ab initio calculations for unveiling all the complexity behind the properties of the model system K2ZnF4:Cu(2+), opening at the same time a window for improving our knowledge on d(9), d(7), or d(4) ions in other layered compounds.

Colour due to Cr3+ ions in oxides: a study of the model system MgO:Cr3+.

Seeking to understand why the cubic centre in MgO:Cr(3+) has the same 10Dq value as emerald, ab initio cluster and periodic supercell calculations have been performed. It is found that the equilibrium Cr(3+)-O(2-) distance, R, in MgO:Cr(3+) is equal to 2.03 Å and thus 0.06 Å higher than that measured for the emerald. Calculations carried out on the isolated CrO(6)(9-) complex at R = 2.03 Å give 10Dq = 14,510 cm(-1), which is 10% smaller than the experimental figure for MgO:Cr(3+). Nevertheless, when the internal electric field, ER(r), due to the rest of the lattice ions is also taken into account, the calculated 10Dq = 16,210 cm(-1) coincides with the experimental value. Accordingly, the colour shift for different oxides doped with Cr(3+) can be well understood on the basis of this extrinsic contribution to 10Dq usually ignored in a ligand field description. The calculated electrostatic potential, VR(r), related to ER(r), is found to be attractive when the electronic density is lying along <110> directions and |r| > 1 Å driven by the first shell of twelve Mg(2+) ions. The action of VR(r) upon the CrO(6)(9-) complex slightly decreases the energy of t2g(xy,xz,yz) orbitals with respect to that for eg(3z(2) - r(2),x(2) - y(2)) orbitals, thus enhancing the 10Dq value by 0.2 eV. However, the addition of VR(r) induces very small changes in the electronic density, a relevant fact that is related to the (2)E(t(2g)(3)) −> (4)A(2)(t(2g)(3)) emission energy being nearly independent of the host lattice along the series of Cr(3+)-doped oxides.

Cr3+-doped fluorides and oxides: role of internal fields and limitations of the Tanabe-Sugano approach.

This work is aimed at clarifying the changes on optical spectra of Cr(3+) impurities due to either a host lattice variation or a hydrostatic pressure, which can hardly be understood by means of the usual Tanabe-Sugano (TS) approach assuming that the Racah parameter, B, grows when covalency decreases. For achieving this goal, the optical properties of Cr(3+)-doped LiBaF(3) and KMgF(3) model systems have been explored by means of high level ab initio calculations on CrF(6)(3-) units subject to the electric field, E(R)(r), created by the rest of the lattice ions. These calculations, which reproduce available experimental data, indicate that the energy, E((2)E), of the (2)E(t(2g)(3)) → (4)A(2)(t(2g)(3)) emission transition is nearly independent of the host lattice. By contrast, the energy difference corresponding to (4)A(2)(t(2g)(3)) → (4)T(1)(t(2g)(2)e(g)(1)) and (4)A(2)(t(2g)(3)) → (4)T(2)(t(2g)(2)e(g)(1)) excitations, Δ((4)T(1); (4)T(2)), is shown to increase on passing from the normal to the inverted perovskite host lattice despite the increase in covalency, a fact which cannot be accounted for through the usual TS model. Similarly, when the Cr(3+)-F(-) distance, R, is reduced both Δ((4)T(1); (4)T(2)) and the covalency are found to increase. By analyzing the limitations of the usual model, we found surprising results that are shown to arise from the deformation of both 3d(Cr) and ligand orbitals in the antibonding e(g) orbital, which has a σ character and is more extended than the π t(2g) orbital. By contrast, because of the higher stiffness of the t(2g) orbital, the dependence of E((2)E) with R basically follows the corresponding variation of covalency in that level. Bearing in mind the similarities of the optical properties displayed by Cr(3+) impurities in oxides and fluorides, the present results can be useful for understanding experimental data on Cr(3+)-based gemstones where the local symmetry is lower than cubic.

Spectrochemical series and the dependence of Racah and 10 Dq parameters on the metal-ligand distance: microscopic origin.

The origin of the spectrochemical series and the different dependence of crystal-field splitting (10Dq) and Racah parameters on the metal-ligand distance, R, is explored through ab initio calculations on Cr(3+)-doped K2NaScF6, Cs2NaYCl6, Cs2NaYBr6, and Cs2NaYI6 lattices. For this purpose both periodic and cluster calculations have been performed. An analysis of ab initio results proves that 10Dq values mostly come from the small admixture of deep nLs ligand orbitals present in the antibonding eg(∼ x(2)-y(2),3z(2)-r(2)) level and not from the dominant covalency with valence nLp ligand orbitals, which is actually responsible for the reduction of Racah parameters. This study thus reveals the microscopic origin of the stronger dependence upon R of 10Dq when compared to that observed for Racah parameters, thus explaining why electronic transitions which are 10Dq-independent give rise to sharp optical bands. As a salient feature, while the covalency with nLp levels increases significantly on passing from CrF6(3-) to CrI6(3-), the nLs admixture in eg is found to be practically unmodified. This fact helps to understand the progressive decrease of 10Dq through the series of CrF6(3-), CrCl6(3-), CrBr6(3-), and CrI6(3-) complexes embedded in the corresponding host lattices when compared at the corresponding equilibrium distance at zero pressure. The growing importance of the nLs admixture is well-depicted using deformation density diagrams on passing from the ground state (4)A2(t2g(3)) to the (4)T2(t2g(2)eg) excited state depicted at several R values.

Tunneling splitting of Jahn-Teller ions in oxides.

The magnitude of tunneling splitting, 3Gamma, that governs decoherence in quantum systems under symmetric potentials, is frequently unknown. Using first-principles calculations, we have obtained 3Gamma for a number of E[symbol:see text]e Jahn-Teller impurities in solids. Calculated values span 6 orders of magnitude on passing from KCl:Ag{2+} to MgO:Cu{2+}. Values associated with Cu2+- and Ag2+-doped MgO are 2 orders of magnitude larger than those previously assumed and consistent with the existence of a dynamic Jahn-Teller effect. The origin and enhancement with pressure of these high 3Gamma values is discussed in detail.

Cr3+ in layered perovskites: do the electron paramagnetic resonance parameters only depend on the impurity-ligand distances?

The actual value of axial, R(ax), and equatorial, R(eq), impurity-ligand distances for Cr(3+) embedded in tetragonal K(2)MgX(4) (X = F, Cl) lattices has been explored by means of density functional theory (DFT) calculations on clusters involving up to 69 ions using two different functionals. For K(2)MgF(4):Cr(3+) R(eq) and R(ax) are found to be coincident within only 0.5 pm. When the g tensor of K(2)MgF(4):Cr(3+) is derived considering only the CrF(6)(3-) unit in vacuo at the calculated equilibrium geometry the g(⊥)-g(||) quantity fails to reproduce the experimental value by one order of magnitude. In contrast, when the active electrons localized in the CrX(6)(3-) complex (X = F, Cl) are allowed to feel the anisotropic electric field coming from the rest of the lattice ions the splitting in the first excited state, (4)T(2), increases by one order of magnitude. The present results thus show that the g tensor anisotropy and the zero-field splitting constant, D, observed for K(2)MgX(4):Cr(3+) (X = F, Cl) are not mainly due to a local deformation of the CrX(6)(3-) octahedron but to the action of the internal electric field, often ignored when seeking the microscopic origin of electronic properties due to impurities in insulating lattices. Accordingly, serious doubts on the validity of the superposition model are cast by the present work.

Pseudo-Jahn-Teller origin of the low barrier hydrogen bond in N(2)H(7) (+).

The microscopic origin and quantum effects of the low barrier hydrogen bond (LBHB) in the proton-bound ammonia dimer cation N(2)H(7) (+) were studied by means of ab initio and density-functional theory (DFT) methods. These results were analyzed in the framework of vibronic theory and compared to those obtained for the Zundel cation H(5)O(2) (+). All geometry optimizations carried out using wavefunction-based methods [Hartree-Fock, second and fourth order Moller-Plesset theory (MP2 and MP4), and quadratic configuration interaction with singles and doubles excitations (QCISD)] lead to an asymmetrical H(3)N-H(+)cdots, three dots, centeredNH(3) conformation (C(3v) symmetry) with a small energy barrier (1.26 kcalmol in MP4 and QCISD calculations) between both equivalent minima. The value of this barrier is underestimated in DFT calculations particularly at the local density approximation level where geometry optimization leads to a symmetric H(3)Ncdots, three dots, centeredH(+)cdots, three dots, centeredNH(3) structure (D(3d) point group). The instability of the symmetric D(3d) structure is shown to originate from the pseudo-Jahn-Teller mixing of the electronic (1)A(1g) ground state with five low lying excited states of A(2u) symmetry through the asymmetric alpha(2u) vibrational mode. A molecular orbital study of the pseudo-Jahn-Teller coupling has allowed us to discuss the origin of the proton displacement and the LBHB formation in terms of the polarization of the NH(3) molecules and the transfer of electronic charge between the proton and the NH(3) units (rebonding). The parallel study of the H(5)O(2) (+) cation, which presents a symmetric single-well structure, allows us to analyze why these similar molecules behave differently with respect to proton transfer. From the vibronic analysis, a unified view of the Rudle-Pimentel three-center four-electron and charge transfer models of LBHBs is given. Finally, the large difference in the N-N distance in the D(3d) and C(3v) configurations of N(2)H(7) (+) indicates a large anharmonic coupling between alpha(2u)-alpha(1g) modes along the proton-transfer dynamics. This issue was explored by solving numerically the vibrational Schrodinger equation corresponding to the bidimensional E[Q(alpha(2u)),Q(alpha(1g))] energy surface calculated at the MP46-311++G(**) level of theory.

Comment on "Molecular structure and dynamics of off-center Cu(2+) ions and strongly coupled Cu(2+)-Cu(2+) pairs in BaF(2) crystals: Electron paramagnetic resonance and electron spin relaxation studies" [J. Chem. Phys. 127, 124705 (2007)].

In the recent study of Cu(2+)-doped BaF(2) Hoffmann et al. demonstrated using electron paramagnetic resonance spectroscopy that the Cu(2+) impurity experiences an off-center shift from the substitutional position and ascribe this distortion to the Jahn-Teller effect. In this comment, we propose that the off-center distortion observed for BaF(2):Cu(2+) is driven by pseudo-Jahn-Teller interactions which are qualitatively different and in competition with the usual Jahn-Teller effect. It is also stressed that off-center phenomena in a given host lattice are not necessarily enhanced by decreasing the ionic radius of the impurity.

Local symmetry change in BaF2:Mn2+ at approximately 50 K: microscopic insight.

The microscopic origin of the abrupt cubic-tetrahedral symmetry change associated with the local a(2u) vibrational mode observed by electron paramagnetic resonance in BaF(2):Mn(2+) at approximately 50 K is explored by means of density functional theory calculations. It is found that while the a(2u) vibrational frequencies calculated for MnF(8) (6-) in CaF(2) (168 cm(-1)) and SrF(2) (132 cm(-1)) are real, in the case of BaF(2):Mn(2+), the adiabatic potential curve along this mode exhibits a double well with a small barrier of 50 cm(-1). Although the ground and first excited vibrational states are localized around the energy minima, the rest of the excited states resemble those of a harmonic oscillator centered at Q(a(2u))=0. Moreover, only the inclusion of the anharmonic coupling between a(2u) and t(1u) modes allows one to understand the T(d)-O(h) transition temperature. It is shown that both the unusually high Mn(2+)-F(-) distance in BaF(2):Mn(2+) and the pseudo-Jahn-Teller interaction of the t(2g)(xy;xz;yz) antibonding orbital with filled t(1u) orbitals favor the a(2u) instability. The calculated a(2u) force constant for different electronic states supports this conclusion.

Microscopic insight into properties and electronic instabilities of impurities in cubic and lower symmetry insulators: the influence of pressure.

This article reviews the microscopic origin of properties due to transition-metal (TM) impurities, M, in insulator materials. Particular attention is paid to the influence of pressure upon impurity properties. Basic concepts such as the electronic localization in an MX(N) complex, the electrostatic potential, V(R), arising from the rest of the lattice ions or the elastic coupling of the complex to the host lattice are initially exposed. The dependence of optical and magnetic parameters on the impurity-ligand distance, R, in cubic lattices is discussed in a first step. Emphasis is put on the actual origin of the R dependence of 10Dq. Examples revealing that laws for strict cubic symmetry cannot in general be transferred to lower symmetries are later given. This relevant fact is shown to come from allowed hybridizations like nd-(n+1)s as well as the influence of V(R). As a salient feature the different colour in ruby and emerald is stressed to arise from distinct V(R) potentials in Al(2)O(3) and Be(3)Si(6)Al(2)O(18). The last part of this review deals with electronic instabilities. The phenomena associated with the Jahn-Teller (JT) effect in cubic lattices, the origin of the energy barrier among equivalent minima and the existence of coherent tunnelling in systems like MgO:Cu(2+) are discussed. An increase of elastic coupling is pointed out to favour a transition from an elongated to a compressed equilibrium conformation. Interestingly the equilibrium geometry of JT ions in non-cubic lattices is shown to be controlled by mechanisms different to those in cubic systems, V(R) playing again a key role. The relevance of first principles calculations for clarifying the subtle mechanisms behind off-centre instabilities is also pointed out. Examples concern monovalent and divalent TM impurities in lattices with the CaF(2) structure. The instability due to the transition from the ground to an excited state is finally considered. For complexes with significant elastic coupling vibrational frequencies and the Stokes shift are expected to undergo bigger changes through a chemical rather than a hydrostatic pressure. The reduction of Huang-Rhys factors upon increasing the pressure is discussed as well.

Impurities in noncubic crystals: stabilization mechanisms for Jahn-Teller ions in layered perovskites.

Mechanisms responsible for the local geometry around Jahn-Teller impurities in K2NiF4 type lattices are shown to be different from those generating the warping in cubic crystals. The present density functional theory calculations reveal that the elastic anisotropy of the host lattice (visible for closed shell impurities) and the electric field created by the rest of lattice ions upon active electrons make it possible to have d(9) ions in an elongated geometry but with a A(1g) ground state. The puzzling difference between equilibrium geometries for Cu2+ and Ni+ in layered perovskites can reasonably be understood.

Fine-needle aspiration biopsy of liver masses: diagnostic value and reproducibility of cytological criteria.

There are many helpful cytological criteria for the diagnosis of liver fine-needle aspiration biopsies (FNABs), but none of them are pathognomonic of primary or metastatic tumors. We analyzed the diagnostic value and reproducibility of 28 cytological parameters in FNABs from 140 hepatic masses, including 29 benign lesions, 49 hepatocellular carcinomas (HCCs), and 62 metastatic tumors, encompassing 48 adenocarcinomas (ACAs). Five different observers evaluated each sample, and the interobserver and intraobserver agreement was studied. Multivariable analysis showed that the criteria more closely associated with malignancy were irregular nuclear contour, three-dimensional cell groups, and atypical naked nuclei. Capillaries separating tumor cells and granular cytoplasm were strongly associated with HCCs, while eccentrically placed nuclei and necrosis were most commonly seen in ACAs and in metastatic tumors. The intraobserver and interobserver agreement was excellent for the final cytological diagnosis, and there was fair to very good interobserver agreement for 22 of the 28 criteria studied. Architectural features were less reproducible than pure cytological criteria. Intraobserver variability was not influenced by the years of experience in the field. A precise and strict definition of terminology rendered a better reproducibility of the cytological criteria.