Small polaron hopping conduction mechanism in Ni-doped LaFeO3

The electrical transport properties of LaFe_{1? x} Ni _x O₃ (0.1 ≤ x ≤ 0.6) bulk samples were investigated over a wide temperature range, i.e. 9–300 K. Powder x-ray diffraction patterns at room temperature showed that all samples were formed in a single phase. However, a structural transformation was observed from orthorhombic (Pnma) to rhombohedral crystal symmetry at x > 0.5 in Ni-doped samples, which is supported by the electrical transport analysis. Temperature-dependent resistivity data were fitted using Mott's variable-range hopping model for a limited range of temperatures to calculate the hopping distance and the density of states at Fermi level. It was found that all parameters vary systematically with an increase in Ni concentration. Moreover, the resistivity data were also fitted using the small polaron hopping (SPH) model. The non-adiabatic SPH conduction mechanism is followed up to 50% Ni concentration, whereas an adiabatic hopping conduction mechanism is active above it. Such a change in the conduction mechanism is accompanied by subtle electronically induced structural changes involving Fe³⁺–O–Fe³⁺ and Fe³⁺–O–Ni³⁺ bond angles and bond lengths. Thus, we suggest that the transport properties can be explained according to the additional delocalization of charge carriers induced by Ni doping.     

Comparison of O–H and C–H activation of methanol on Ni-based cluster: a DFT investigation

Using the density functional theory, the initial dehydrogenation of methanol on Ni_xM_y (M?=?Ni, Co, Fe, Mn, Cr, x?+?y?=?4, y?=?1, 2) clusters is investigated. Two adsorption and dehydrogenation mechanisms of methanol are studied: one proceeds along the C–H scission and another begins with the breaking of the O-H bond. The adsorption sites of methanol on the Ni or M sites of the Ni_xM_y clusters are considered. The adsorption of methanol on Ni₄ cluster is stronger than those on bimetallic clusters, while the initial dehydrogenation barriers on Ni_xM_y clusters are lower than that on Ni₄ cluster. The comparable energy barriers of two pathways (O–H or C–H dissociation) on Ni-based clusters indicate that these two paths are quite competitive. In addition, the Ni₂M₂ clusters show superior activation performance compared with the Ni₃M clusters, especially for Ni₂Mn₂ and Ni₂Cr₂ clusters. The effects of alloyed metal on the catalytic activity of Ni for methanol initial dehydrogenation, including the adsorption energy, O–H or C–H bond scission barrier and frontier molecular orbital levels, are discussed. It can be concluded that the addition of Co, Fe, Mn and Cr to Ni catalyst is able to enhance the activity of the methanol dehydrogenation reaction.     

Theoretical explanation of optical absorption spectra and covalent effect of Ni2+ ions in octahedral sites of Ca3Sc2Ge3O12 crystal

The optical absorption spectra (d-d transition bands) and covalent effect of Ni²⁺ ions in octahedral sites of Ca₃Sc₂Ge₃O₁₂ crystal have been investigated by the full energy matrix based on the two spin–orbit coupling parameters model. The bond length of octahedral site is R_i?=?2.19 Å, which can be determined by the cubic crystal-field parameter and optical spectral data. The lattice distortion of the Ni²⁺ center in Ca₃Sc₂Ge₃O₁₂ crystal is also obtained from the calculations. In addition, the result has shown that the covalent effect of Ni²⁺ ion in the octahedral site of Ga₃Sc₂Ge₃O₁₂ is obvious and cannot be ignored. The calculated d-d transition bands agree well with that of the experimental findings, suggesting that the present methods can explain reasonably the optical spectral data and covalent effect of 3d⁸ ions in octahedral lattices.     

Methane dehydrogenation on monomeric Rh center located on (100) γ-alumina — A theoretical study

The reaction mechanism of methane dehydrogenation on monomeric Rh center located on (100) γ-alumina has been theoretically investigated at the PBE0/cc-pVTZ, SDD level. The (100) face of γ-alumina support is represented by an Al₈O₂₆H₂₈ cluster, which is cut out from the ideal crystal structure. Then, two model Rh/γ-Al₂O₃ catalysts, in which Rh center interacts with one oxygen or two oxygen atoms of the (100) surface of γ-Al₂O₃, have been compared and denoted as Rh/Al₈O₂₆H₂₇ and Rh/Al₈O₂₆H₂₆, respectively. Toward methane activation, the model catalyst Rh/Al₈O₂₆H₂₇ exhibits better performance than Rh/Al₈O₂₆H₂₆. For the first CH bond cleavage of methane, the lowering of activation barriers on Rh/Al₈O₂₆H₂₇ is mainly caused by lower substrate activation strain ΔE^≠_strain[substr], which is from substrate equilibrium geometry to the geometry it adopts in the TS, in comparison with that on Rh/Al₈O₂₆H₂₆. These results are in qualitative agreement with the experimental results, where the partially reduced Rh⁺ is one of the active sites for methane dissociation.     

Computational study on structures,thermochemical properties,and bond energies of disulfide oxygen (S–S–O)‐bridged CH3SSOH and CH3SS(=O)H and radicals

Cleavage of disulfide bonds is a common method used in linking peptides to proteins in biochemical reactions. The structures, internal rotor potentials, bond energies, and thermochemical properties (Δ_fH°, S°, and Cp(T)) of the S–S bridge molecules CH₃SSOH and CH₃SS(=O)H and the radicals CH₃SS?=O and C?H₂SSOH that correspond to H‐atom loss are determined by computational chemistry. Structure and thermochemical parameters (S° and Cp(T)) are determined using density functional Becke, three‐parameter, Lee–Yang–Parr (B3LYP)/6‐31++G (d, p), B3LYP/6‐311++G (3df, 2p). The enthalpies of formation for stable species are calculated using the total energies at B3LYP/6‐31++G (d, p), B3LYP/6‐311++G (3df, 2p), and the higher level composite CBS–QB3 levels with work reactions that are close to isodesmic in most cases. The enthalpies of formation for CH₃SSOH, CH₃SS(=O)H are ?38.3 and ?16.6 kcal mol^?1, respectively, where the difference is in enthalpy RSO–H versus RS(=O)–H bonding. The C–H bond energy of CH₃SSOH is 99.2 kcal mol^?1, and the O–H bond energy is weaker at 76.9 kcal mol^?1. Cleavage of the weak O–H bond in CH₃SSOH results in an electron rearrangement upon loss of the CH₃SSO–H hydrogen atom; the radical rearranges to form the more stable CH₃SS· = O radical structure. Cleavage of the C–H bond in CH₃SS(=O)H results in an unstable [CH₂SS(=O)H]* intermediate, which decomposes exothermically to lower energy CH₂ = S + HSO. The CH₃SS(=O)–H bond energy is quite weak at 54.8 kcal mol^?1 with the H–C bond estimated at between 91 and 98 kcal mol^?1. Disulfide bond energies for CH₃S–SOH and CH3S–S(=O)H are low: 67.1 and 39.2 kcal mol^?1. Copyright © 2011 John Wiley & Sons, Ltd.     

The adsorption and reaction of ethylene glycol and 1,2-propanediol on Pd(111): A TPD and HREELS study

The reactions of ethylene glycol and 1,2-propanediol have been studied on Pd(111) using temperature programmed desorption (TPD) and high resolution electron energy loss spectroscopy (HREELS). Both molecules initially decompose through O–H activation, forming ethylenedioxy (–OCH₂CH₂O–) and 1,2-propanedioxy (–OCH₂CH(CH₃)O–) surface intermediates. For ethylene glycol, increases in thermal energy lead to dehydrogenation and formation of carbonyl species at both oxygen atoms. The resulting glyoxal (O═CHCH═O) either desorbs molecularly or reacts through one of two competing pathways. The favored pathway proceeds via C–C bond scission, dehydrogenation, and decarbonylation to form carbon monoxide and hydrogen. In a minor pathway, small amounts of glyoxal undergo C–O bond scission and recombination with surface hydrogen to form ethylene and water. The same reaction mechanism occurs for 1,2-propanediol after methyl elimination and formation of glyoxal. However, this is accompanied by a minor pathway involving a methylglyoxal (O=CHC(CH₃)=O) intermediate. The prevalence of the dehydrogenation/decarbonylation pathway in the current work is consistent with the high selectivity for C–C scission in the aqueous phase reforming of polyols on supported Pd catalysts.     

Can 2‐acylpyrroles form an intramolecular hydrogen bond?

The formation of intramolecular hydrogen bonding by certain N‐substituted 2‐acylpyrroles has been demonstrated by B3LYP/aug‐cc‐pVDZ calculations, the quantum theory of atoms in molecules, and the natural bond orbital method. Total electron energy densities H_BCP at the bond critical point of the H?O bond were applied to analyze the strength of these interactions. The relations between quantum theory of atoms in molecules, carbonyl stretching vibrational modes ν_{C = O}, and natural bond orbital parameters associated with the formation of the C–H?O interaction have been established. The short contacts were found experimentally in the crystal structure of a new 2‐acylpyrrole derivative 5‐chloro‐2‐oxopentyl‐1‐(5‐chloro‐2‐oxopentyl)pyrrolo‐2‐carboxylate. The influence of 2‐ and N‐substitution of 2‐acylpyrroles on C‐H?O interaction energy is discussed. It was found that the methylene group may act as a proton donor leading to a red‐shift or blue‐shift phenomenon of the ν_C–H stretching mode. Copyright © 2015 John Wiley & Sons, Ltd.     

La0.8Sr0.2Ni0.4Fe0.6O3–Ce0.8Gd0.2O2–δ Nanocomposite as Mixed Ionic–Electronic Conducting Material for SOFC Cathode and Oxygen Permeable Membranes: Synthesis and Properties

Mixed ionic–electronic conducting nanocomposite La_0.8Sr_0.2Ni_0.4Fe_0.6O₃ (LSNF)–Ce_0.8Gd_0.2O_{2– δ} (GDC) was prepared via ultrasonic dispersion of nanocrystalline powders of perovskite and fluorite oxides in water with addition of surfactant, followed by drying and sintering up to 1300°C. Analysis of the real structure of nanocomposite (studied by XRD and TEM with EDX) and its surface composition (studied by XPS) revealed moderate redistribution of elements between phases favoring their epitaxy. Results of impedance spectroscopy, oxygen isotope exchange, O₂ TPD and H₂ TPR experiments revealed a positive effect of composite interfaces on the oxygen mobility and reactivity agreeing with the ambipolar transport behavior of MIEC composite. Preliminary testing of button-size cell with functionally graded LSNF–GDC cathode layer supported on thin YSZ layer covering Ni/YSZ cermet demonstrated high and stable performance, which is promising for its practical application.     

Etude par spectroscopie de photoelectrons des interactions metal—support dans des catalyseurs a l'iridium depose sur des oxydes metalliques

Several iridium supported catalyst were studied by means of x-ray photoelectron spectroscopy. These catalysts contain 5 wt. % iridium impregnated from aqueous solution of hexachloroiridic acid on δ-alumina, silica, zinc oxide, titanium oxide and Ketjen silica alumina and are used in catalytic oxidation of olefins.Photoelectron spectra of oxides, impregnated oxides and hydrogen reduced catalysts have been recorded. Chemical shifts observed on impregnated oxides indicate that alumina and titanium oxide make possible the reduction of some of the hexachloroiridates ions into an iridium(III) chloro complex. This reaction is not detected with zinc oxide and silica.For the reduced catalysts, the iridium 4f doublet is shifted to higher binding energies with respect to that of unsupported iridium and the iridium lines have an anomalous breadth. We have postulated that an electronic interaction occurs between the support acting as an electron acceptor and the metal acting as an electron donor. The chemical shifts depend on the nature of the support, increasing ZnO < SiO₂ < TiO₂ < Al₂O₃, and may be correlated with the Fermi level in the metallic oxide. With silica-alumina and progressively de-aluminated silica-alumina, a simultaneous variation of the iridium chemical shift and catalytic activity is observed.     

Dynamic 1H NMR investigation along with a theoretical study around the C–C and C = C bonds in a particular phosphorus ylide

In the present work, the dynamic ¹H NMR effects were investigated at variable temperatures within a particular phosphorus ylide involving a 2‐benzoxazolinone around the carbon–carbon single bond and also partial carbon–carbon double bond in two Z‐ and E‐rotational isomers. Activation and kinetic parameters including ΔH^≠, ΔG^≠, ΔS^≠ and E_a were determined in accord with the dynamic ¹H NMR data for three rotational processes. In addition, theoretical studies based upon rotation around the same bonds were investigated using ab initio and DFT methods at the HF/6‐31G(d,p) and B3LYP/6‐31G(d,p) levels of theory. Theoretical activation and kinetic parameters including ΔH^≠, ΔG^≠, ΔS^≠ and E_a were calculated at 298 K and experimental temperatures for five rotational processes. These results (experimental and theoretical), taken together, indicate that the rotational energy barrier around the C = C double bond was considerably high and the observation of the two rotational isomers was impossible (seen as a single isomer) at the high temperatures, in this case rotation around the C = C bond was too fast on the NMR time scale. When the temperature was relatively low, the rate of rotation was sufficiently slow; therefore, observation of the two Z‐ and E‐isomers was possible. In addition, calculations at the HF/6‐31G(d,p) level of theory showed very favorable results in agreement with the experimental data on rotation around the C = C bond. While, B3LYP level using the 6‐31G(d,p) basis set was provided the reasonable data for the restricted rotations around the C–C and C–N single bond. Copyright © 2012 John Wiley & Sons, Ltd.     

<Superscript>1</Superscript>H NMR study of molecular dynamics of acetylcholine chloride

The longitudinal relaxation timeT ₁ and the second momentM ₂ of¹H nuclear magnetic resonance line in a wide temperature range have been measured for acetylcholine chloride. Two different types of the methyl groups reorientation occurred. The first type was the hindered rotation of the methyl group denoted as C(1)H₃ about the threefold symmetry axis. The second type was the reorientation of the trimethyl group-N(CH₃)₃ around the pseudo C₃^′ axis of C(6)-N(7) bond, which accompanied the standard C₃ motion of the methyl group. The Dunn-McDowell model was applied to analyze the dynamics observed.     

Effect of temperature on lithium-ion intercalation kinetics of LiMn1.5Ni0.5O4-positive-electrode material

LiMn_1.5Ni_0.5O₄ is synthesized by a sol–gel method and the intercalation kinetics as positive electrode for lithium-ion batteries is investigated by EIS. LiMn_1.5Ni_0.5O₄ particles prepared via sol–gel process possess spinel phase with Fd-3m space group. The charge-transfer resistance, the exchange-current density and the solid-phase diffusion are found as a function of temperature. The apparent activation energy of the exchange current, the charge transfer, and the lithium diffusion in solid phase are also determined, respectively. This result indicates that the effect of the temperature on the cell capacity and the current dependence of the capacity results mainly from the enhancement of the lithium diffusion at elevated temperatures. It can be concluded that LiMn_1.5Ni_0.5O₄ cell has a bad rate cycling performance at elevated temperatures before any modification due to the high diffusion apparent activation energy. The relevant theoretical elucidations thus provide us some useful insights into the design of novel LiMn_1.5Ni_0.5O₄-based positive-electrode materials.     

Chemically triggered C–ON bond homolysis in alkoxyamines. Part 7. Remote polar effect

In a recent work (Org. Lett. 2012, 14, 358–361), we showed that the activation by benzylation of alkoxyamine 1 (diethyl (1‐(tert‐butyl(1‐(pyridin‐4‐yl)ethoxy)amino)‐2,2‐dimethylpropyl)phosphonate) afforded a surprisingly large C–ON bond homolysis rate constant k_d. Taking advantage of the easy preparation of para‐X‐benzyl‐activated alkoxyamines 2 and of the presence of a shielding methylene group between the two aromatic moieties, we investigated the long range (10 bonds between the X group and the C–ON bond) polar effect for X = H, F, OMe, CN, NO₂, NMe₂, ⁺NHMe₂,Br^?. It was observed that the effect was weak (4‐fold) and mainly due to the zwiterionic mesomeric forms generated by the presence of group X on the para position, i.e. k_d increased for CN and NO₂ and decreased for OMe, NMe₂ and ⁺NMe₂H,Br^?. DFT calculations at the B3LYP/6‐31G(d,p) level were performed to determine orbital interactions (natural bond orbital (NBO) analysis), Mulliken and NBO charges which support the reactivity described. Copyright © 2014 John Wiley & Sons, Ltd.     

Structures and binding energies for complexations of different spin states of Ni+ and Ni2+ to aromatic molecules

Abstract

Density functional theory calculations, using the B3LYP parameterisation, were performed to determine structures, vibrational frequencies, and binding energies for complexation of Ni⁺ and Ni²⁺ cations with benzene and naphthalene molecules and clusters. The calculations employed the Stuttgart basis set with ECP pseudo potentials for the Ni cations and basis sets of at least triple ζ plus polarisation, and diffuse quality for C and H. The effect of electron correlation on non-bonded interactions was accounted for by the Grimme GD3 dispersion correction. Counterpoise computations were made for BSSE. Comparison between experiment and theory provide fascinating new insight into the bonding for these prototypical organometallic (OM) complexes. These structures have a sandwich topology, indicating major structural reorganisations occuring when benzene or naphthalene interact with Ni cations. Adiabatic electron affinities and ionisation potentials agree well with experiment when available. Binding energies were also determined, providing insight into the stability of the complexes. The results presented here provide important information for future studies to address additional investigations of both problems of the electronic structure properties of these complexes, as well as the role of the polycyclic aromatic hydrocarbons (PAHs) in the interstellar medium (ISM) and soot formation in combustion. The Ni⁺/Ni²⁺ + aromatic organometallic bonding is of the same order of stability as an aromatic C–H bond. Such bonding modifies the IR spectrum of the complexed aromatic molecules by enhancing the 3.3?μm feature and decreasing the C–H bands in the 11–12?μm range (γ C–H). Organometallic complexation reactions may contribute significantly to metal depletion in the ISM.     

Effect of γ-Al2O3 substrate on NO2 interaction with supported BaO clusters

BaO oxide is the main storage component of the NO_x storage and reduction catalysts. Herein, the interactions between the NO₂ molecule and the unsupported as well as γ-Al₂O₃ supported BaO clusters have been studied using the first principle density functional theory calculation. Our results indicated that there is a strong synergetic effect involving both the BaO clusters and the surface of the γ-Al₂O₃ substrate toward NO₂ adsorption. The interfacial region between the monodispersed BaO cluster and the substrate surface that allows NO₂ to bond with the cluster and the surface simultaneously was shown to be optimal for NO₂ adsorption.     

In situ observation of Ni–Mo–S phase formed on NiMo/Al2O3 catalyst sulfided at high pressure by means of Ni and Mo K‐edge EXAFS spectroscopy

To obtain direct evidence of the formation of the Ni–Mo–S phase on NiMo/Al₂O₃ catalysts under high‐pressure hydrodesulfurization conditions, a high‐pressure EXAFS chamber has been constructed and used to investigate the coordination structure of Ni and Mo species on the catalysts sulfided at high pressure. The high‐pressure chamber was designed to have a low dead volume and was equipped with polybenzimidazole X‐ray windows. Ni K‐edge k³χ(k) spectra with high signal‐to‐noise ratio were obtained using this high‐pressure chamber for the NiMo/Al₂O₃ catalyst sulfided at 613 K and 1.1 MPa over a wide k range (39.5–146 nm^?1). The formation of Ni–Mo and Mo–Ni coordination shells was successfully proved by Ni and Mo K‐edge EXAFS measurement using this chamber. Interatomic distances of these coordination shells were almost identical to those calculated from Ni K‐edge EXAFS of NiMo/C catalysts sulfided at atmospheric pressure. These results support the hypothesis that the Ni–Mo–S phase is formed on the Al₂O₃‐supported NiMo catalyst sulfided under high‐pressure hydrodesulfurization conditions.     

Theoretical studies of absorption spectra and microstructure of Ni2+ at the octahedral site of the NiFe2O4 nanoparticle

The optical absorption spectra, microstructure and electronic spin resonance parameters (electronic spin resonance (ESR) g factor) for Ni²⁺ ions at octahedral centers of nickel ferrite nanoparticles are calculated from the two-spin–orbit-parameter model. The effect of spin–orbital coupling of the central metal 3d⁸ ions and ligand oxygen ions has been taken into account in the full energy matrix and ESR g formula. The calculated results are in good agreement with the observed values. In addition, the microstructures of Ni²⁺ ions at octahedral centers in NiFe₂O₄ are reasonably determined from the calculations.     

Theory of chemical bonds in metalloenzymes XXII: a concerted bond-switching mechanism for the oxygen–oxygen bond formation coupled with one electron transfer for water oxidation in the oxygen-evolving complex of photosystem II

ABSTRACT

QM(UB3LYP)/MM(AMBER) calculations were performed for the locations of the transition structure (TS) of the oxygen–oxygen (O–O) bond formation in the S₄ state of the oxygen-evolving complex (OEC) of photosystem II (PSII). The natural orbital (NO) analysis of the broken-symmetry (BS) solutions was also performed to elucidate the nature of the chemical bonds at TS on the basis of several chemical indices defined by the occupation numbers of NO. The computational results revealed a concerted bond switching (CBS) mechanism for the oxygen–oxygen bond formation coupled with the one-electron transfer (OET) for water oxidation in OEC of PSII. The orbital interaction between the σ-HOMO of the Mn(IV)₄–O₍₅₎ bond and the π*-LUMO of the Mn(V)₁=O₍₆₎ bond plays an important role for the concerted O–O bond formation for water oxidation in the CaMn₄O₆ cluster of OEC of PSII. One electron transfer (OET) from the π-HOMO of the Mn(V)₁=O₍₆₎ bond to the σ*-LUMO of the Mn(IV)₄–O₍₅₎ bond occurs for the formation of electron transfer diradical, where the generated anion radical [Mn(IV)₄–O₍₅₎]^-? part is relaxed to the ?Mn(III)₄?…?O₍₅₎^- structure and the cation radical [O₍₆₎=Mn(V)₁]⁺ ? part is relaxed to the ⁺O₍₆₎–Mn(IV)₁? structure because of the charge-spin separation for the electron-and hole-doped Mn–oxo bonds. Therefore, the local spins are responsible for the one-electron reductions of Mn(IV)₄->Mn(III)₄ and Mn(V)₁->Mn(IV)₁. On the other hand, the O₍₅₎^- and O₍₆₎⁺ sites generated undergo the O–O bond formation in the CaMn₄O₆ cluster. The Ca(II) ion in the cubane- skeleton of the CaMn₄O₆ cluster assists the above orbital interactions by the lowering of the orbital energy levels of π*-LUMO of Mn(V)₁=O₍₆₎ and σ*-LUMO of Mn(IV)₄–O₍₅₎, indicating an important role of its Lewis acidity. Present CBS mechanism for the O–O bond formation coupled with one electron reductions of the high-valent Mn ions is different from the conventional radical coupling (RC) and acid-base (AB) mechanisms for water oxidation in artificial and native photosynthesis systems. The proton-coupled electron transfer (PC-OET) mechanism for the O–O bond formation is also touched in relation to the CBS-OET mechanism.     

Atmospheric chemistry of HFE-7000 (i-C3F7OCH3) and isofluoro-propyl formate (i-C3F7OC(O)H): reactions with OH radicals,atmospheric lifetime and fate of alkoxy radical (i-C3F7OCH2O•) – a DFT study

ABSTRACT

The mechanism of hydrogen abstraction reaction between HFE-7000 (i-C₃F₇OCH₃) and OH radicals using M06-2X functional in conjunction with 6-31+G(d,p) basis set is investigated. The pre-reactive and post-reactive complexes from intrinsic reaction coordinate calculations are validated at entrance and exit channels, respectively. The standard enthalpies of formation for the species and bond dissociation energy for C–H bond are also estimated. The rate constants of the titled reactions over the temperature range of 250–450 K are reported. The OH-driven atmospheric life time of i-HFE-7000 is computed to be 3.19 years. The atmospheric fate of the alkoxy radical (i-C₃F₇OCH₂O^?) is also explored here for the first time. Three prominent plausible decomposition channels including oxidation are considered in detail. The thermochemical data reveal that reaction with O₂ is the dominant path for the decomposition of i-C₃F₇OCH₂O^? radical. Moreover, rate constant for the OH-initiated hydrogen abstraction of isofluoro-propyl formate (i-C₃F₇OC(O)H) is also reported.     

Stoichiometry of LiNiO2 Studied by Mössbauer Spectroscopy

From the ⁶¹Ni and ⁵⁷Fe Mössbauer spectroscopy data follows the cationic site assignment in Li_1–x Ni_1+x O₂. Our data explain the ferromagnetic properties of this material because of the appearance of Ni²⁺ (S=1) among Ni³⁺ (S=1/2) in Ni³⁺O₂ hexagonal planes. We have no evidence for the ferromagnetic interaction between the NiO₂ layers through the excess Ni²⁺ ions substituting the Li⁺ ions. The presence of Ni²⁺ found in the Ni³⁺O₂ planes explains the absence of the Jahn–Teller distortions probably because of the electronic transfer between the Ni³⁺ and Ni²⁺ ions.