Preparation and structural studies of lithium substituted nickel phosphorus trisulphide,Li2NiP2S6

Crystals of Li₂NiP₂S₆ may be prepared by direct combination of stoichiometric amounts of Li₂S, phosphorus, nickel and sulphur in a temperature gradient towards 750°C. The structure determined by X-ray powder diffraction is monoclinic C2/m with $\text{a = 5.926}\text{A}\text{?}\text{, b = 10.917}\text{A}\text{?}\text{, c = 6.718}\text{A}\text{?}\text{, β = 104.4°}$, and is based on the NiPS₃ layer structure with two Ni atoms substituted by lithium, and with two lithium atoms in the van der Waals gap.     

An X-ray photoelectron spectroscopic study of some nickel (II) amine complexes

The X-ray photoelectron (XPS) spectra of several Ni(II) diamine complexes, a Ni(II) triamine complex and several Ni(II) diimine complexes are reported in terms of the Ni 2p, Cl 2p and N 1s core level binding energies. Theoretical models are presented to account for the quadratic relationship observed between XPS Ni 2p_{$\text{3}\text{2}$}binding energy shifts and the N-H infrared rocking frequency as related to these complexes. On the basis of this correlation, it is possible to discriminate between free counter-ions coordinated to the metal or involved in cluster-ion formation. Individual XPS data for these complexes are interpreted in terms of the intrinsic nature of the metal environment and an attempt is made to calculate the metal and donor nitrogen atomic charges for selected complexes.     

ESCA study of Ni(II) dithiocarbazato complexes

N 1s, S 2p and Ni 2p_3/2 binding energies for the Ni(II) dithiocarbazates and N 1s and S 2p binding energies for the methyl esters of dithiocarbazic acids were measured. It was found that the band width of N 1s narrows on going from the esters to the complexes, thus suggesting a closer similarity between the two nitrogen atoms as a consequence of coordination. S 2p binding energies were found to be similar in the above complexes independent of the chromophore present in them. A possible explanation is suggested for this unusual result.     

Bond cutting in K‐doped tris(8‐hydroxyquinoline) aluminium

A series of Al 2p, K 2p, O 1s and N 1s core‐level spectra have been used to characterize the interaction between potassium (K) and tris(8‐hydroxyquinoline) aluminium (Alq₃) molecules in the K‐doped Alq₃ layer. All core‐level spectra were tuned to be very surface sensitive in selecting various photon energies provided by the wide‐range beamline at the National Synchrotron Radiation Research Center, Taiwan. A critical K concentration (x = 2.4) exists in the K‐doped Alq₃ layer, below which the K‐doped atoms generate a strained environment near the O and N atoms within 8‐quinolinoline ligands. This creates new O 1s and N 1s components on the lower binding‐energy side. Above the critical K coverage, the K‐doped atoms attach the O atoms in the Al—O—C bonds next to the phenoxide ring and replace Al—O—C bonds by forming K—O—C bonds. An Alq₃ molecule is disassembled into Alq₂ and Kq by bond cutting and bond formation. The Alq₂ molecule can be further dissociated into Alq, or even Al, through subsequent formations of Kq.     

Azobenzene-functionalized alkanethiols in self-assembled monolayers on gold

Self-assembled monolayers (SAMs) of 4-trifluoromethyl-azobenzene-4′-methyleneoxy-alkanethiols (CF₃– C₆H₄–N=N–C₆H₄–O–(CH₂) _n –SH on (111)-oriented poly-crystalline gold films on mica were examined by X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS). The spectra are analyzed with the help of density-functional-theory calculations of the isolated molecule. Only one doublet is detected in the sulphur 2p spectra of the investigated SAMs, consistent with a thiolate bond of the molecule to the gold surface. The C 1s XP spectra and the corresponding XAS π ^* resonance exhibit a rich structure which is assigned to the carbon atoms in the different chemical surroundings. Comparing XPS binding energies of the azobenzene moiety and calculated initial-state shifts reveals comparable screening of all C 1s core holes. While the carbon 1s XPS binding energy lies below the π ^*-resonance excitation-energy, the reversed order is found comparing core ionization and neutral core excitation of the nitrogen 1s core-hole of the azo group. This surprising difference in core-hole binding energies is interpreted as site-dependent polarization screening and charge transfer among the densely packed aromatic moieties. We propose that a quenching of the optical excitation within the molecular layer is thus one major reason for the low trans to cis photo-isomerization rate of azobenzene in aromatic-aliphatic SAMs.     

Infrared studies of lithium intercalation in the FePS3 and NiPS3 layer-type compounds

Infrared spectra (700-30 cm^-1) of several lithium intercalates (chemically prepared) Li_xMPS₃, with M=Fe, Ni and 0<x<1.5, have been recorded and compared with those known for the corresponding host lattices. These lithium intercalates are mainly characterized by new absorption bands at 336 cm^-1 and 310 cm^-1 for the iron and nickel compounds, respectively. These bands assigned to lithium vibrations increase progressively with lithium content : it is concluded that Li⁺ ions are more likely to occupy the 2d and 4h “octahedral” sites in the gaps. In addition, the spectra of the nickel derivatives reveal some geometric distortion within the layers and a progressive strengthening of the Ni-S interactions. These results are correlated to the best energy yields obtained in NiPS₃/lithium batteries.     

X-ray photoelectron investigation of charge distribution in copper(II) phthalocyanine complexes

The charged states of atoms in unsubstituted copper(II) phthalocyanine (CuPcH₁₆) and hexade-cafluorinated copper(II) phthalocyanine (CuPcF₁₆) complexes and in thin films of them deposited on silicon substrates by vacuum thermal evaporation are investigated by X-ray photoelectron spectroscopy (XPS). The C(1s), N(1s), Cu(2p) core level energies and the charged states of atoms in the studied complexes are calculated using the DFT method. The performed experimental study and theoretical calculations show that the introduction of electron acceptor substituents into benzene rings mostly affects the atoms of benzene rings and insignificantly affects the charge state of nitrogen atoms in the pyrrole ring.     

Surface properties of LiCoO2, LiNiO2 and LiNi1−xCoxO2

The surface composition and chemical environment of LiCoO₂, hexagonal LiNiO_2, cubic LiNiO₂, and the mixed transition metal oxide LiNi_0.5Co_0.5O₂ have been determined by Auger electron and X-ray photoelectron spectroscopies. While the LiCoO₂ surface properties can easily be extrapolated from bulk composition, the nickel-containing materials are less straightforward. Their surface concentration tends to be depleted in lithium relative to that of the bulk and shows an atypical chemical environment for the constituent elements. The Ni 2p XPS photoemission suggests a near “ NiO-like” selvedge through the XPS binding energies and satellite structure which are essentially identical to that of NiO; the spectrum appears fairly insensitive to lithium concentration. Although there is little evidence for higher binding energy Ni³⁺ species or for an electron poor Ni^2.δ+-derived band structure in the XPS, the lattice oxygen is very electron-rich and yields among the lowest binding energies reported for a transition metal oxide. The nickel-containing lithium oxide selvedge is thus not simply “NiO” and the surface lithium cations have a measurable effect on the electronic structure even in their more highly depleted levels. This is explained in the context of the charge-transfer model of the oxide band structure.     

Auger parameters of ternary Pd–Ni–P amorphous alloys

A series of bulk ternary amorphous alloys of Pd_{100?3 x} Ni_{2 x} P _x were prepared and their amorphicity checked by X-ray diffraction (XRD) and neutron scattering. Auger parameters of these alloys have been derived from X-ray photoelectron spectroscopy (XPS) and X-ray excited Auger electron spectra (AES). Experiments of XPS and AES on each elemental metal and Ni₂P were also performed for comparison. The results show a clear compositional dependence for the 3d binding energies and the MNN Auger energies of Pd on alloying, while Ni 2p core levels and the Ni LMM Auger lines show a weaker variation. Analysis of the data using “excited atom” models indicates electron transfer from Pd, with P carrying negative charge, but the differences in behaviour of the two metallic species suggests that covalent bonding changes may be significant.     

X-ray photoelectron spectroscopy of boron implanted 4145 steel surface

The near-surface region of 4145 steel following boron implantation was investigated by x-ray photoelectron spectroscopy (XPS). The steel surface was implanted with¹¹B⁺ ions to a constant dose of 1.0×10¹⁷ ions cm^–2 at energies of 30 and 135 keV. The XPS spectrum of the implanted surface showed a shift in the B(1s) level towards the higher binding energy. The observed 188.0 eV binding energy of the B(1s) level was found to be in good agreement with the characteristic binding energy of the B(1s) level corresponding to iron boride (Fe₂B). Hence the increase in surface hardness reported previously is related to the formation of an iron boride layer in the near-surface region known for its hardening capabilities.     

Photoelectron-spectroscopic study of nickel,manganese and cobalt selenides

Photoelectron-spectroscopic studies (XPS and UPS) have been carried out to investigate electronic structure and chemical bonding in the monoselenides of nickel, manganese and cobalt. Binding-energy values and chemical shifts are reported from the XPS measurements for Ni 2p and 3s, Mn 2p and 3s, Co 2p and 3s and Se 3p and 3d. The electronic structure and bonding in the monoselenides are interpreted from an analysis of the valence-band spectra. The combined XPS and UPS data suggest transfer of electrons from the metal orbitals (Ni, Mn and Co) to selenium, contrary to bonding schemes proposed previously in the literature. Magnetic-susceptibility measurements performed by us indicate NiSe to be diamagnetic and MnSe and CoSe to be highly paramagnetic at room temperature. The presence of shake-up satellites in the XPS spectra for MnSe and CoSe and their absence for NiSe are discussed in relation to these magnetic properties.     

On the core electron binding energy of carbon and the effective charge of the carbon atom

From Mulliken population data based on ab initio calculations of a series of substituted aromatic compounds and from well-calibrated XPS data (core electron binding energies, E_b) an empirical relation between E_b(C1s) and the charge on the carbon atoms, q_c, has been found: E_b(C1s = 6.42q_c + 4.52q²_c + 285.8 (eV). It is also found that XPS data for other carbon-containing species, notably the cyanide ion, can be described by this relation.     

X-ray photoelectron spectroscopy of copper compounds

The X-ray photoelectron spectra of some forty-six copper compounds and complexes have been measured. The chemical shifts obtained from accurate determinations of the binding energies have been qualitatively explained on the basis of the Pauling electronegativity concept using the group electronegatives of Huheey for the polyatomic counter anions. The chemical shifts of the copper atoms as well as the atoms in the ligands were found to be dependent not only on the oxidation state but also on the kind and number of ligand atoms.

Intense satellite lines were found in the 2p and 2s bands of the cupric compounds; the number and splitting of the satellites were found to be sensitive to the chemical environment. A correlation was found between the satellite splitting and the binding energies and this is explained by a 3d→4s, 4p ‘shake-up’ mechanism.     

Heat of mixing in HfCxN1−x compounds from XPS core level binding energy shifts

The XPS core level binding energies for the Hf4f_{$\text{7}\text{2}$}, Cls and Nls level in several nearly stoichiometric HfC_xN_1?x compounds are reported. Using the thermochemical model to calculate core level binding energy shifts in metals the heat of mixing as function of the HfC/HfN ratio is calculated from the position of the Cls binding energies. In addition it is shown that the Hf4f_{$\text{7}\text{2}$} and Nls binding energies can be used to obtain further thermochemical data for these compounds.     

Accurate core binding energies of ions from Dirac-Fock calculations combined with experimental atomic binding energies

Core binding energies are reported for the singly-charged alkali ions obtained by removing the outer s electron and for the singly-charged halide ions obtained by adding a P_{$\text{3}\text{2}$} electron. The levels studied are Li 1s, Na 1s, K 2p, Rb 3p, Cs 3d, F 1s, Cl 2p, Br 3p and I 3d. The binding energies were obtained by combining DiracF?ock ΔSCF binding-energy shifts between the ions and the corresponding isoelectronic rare gases with experimental rare-gas binding energies, and also by combining the calculated atomīon shifts with experimental atomic binding energies where available. It is shown that the former approach corrects accurately for the correlation energy, which is not included in single-configuration calculations.     

Valence and core state modifications in Pt3Ti

XPS data for the valence band, the Pt 4? states, and the Ti 2p states are presented for the intermetallic Pt₃Ti. Relative to the Pt valence band, the Pt₃Ti band shows a decrease in the density of states just below the Fermi level and a shift of the centroid to higher (binding) energy. Ti 2p and Pt 4? binding energies showed relatively large shifts with respect to the pure metals. These changes in the valence band density of states and core level binding energies are interpreted as arising from hybridization of the d-orbitals in both metals to form strong intermetallic bonds.     

NMR investigation of the layered transition metal phosphorus trichalcogenides and the intercalation compounds LixNiPS3

The transition metal phosphorus trichalcogenides MPX₃ are layered semiconductors which can be intercalated either chemically or electrochemically by lithium atoms. We present a NMR study of the magnetic properties of the MPX₃ compounds (M = Ni, Mn, Fe; X = S, Se) and their modification as a function of intercalation in the compounds Li_xNiPS₃ (x = 0 ? 1.29). In the concentration range x = 0.02 ? 0.5, the relative shift of the P³¹ resonance line K_iso = -0.052 % and the Neel temperature T_N = 155 K are constant and barely different from that measured in pure NiPS₃ (K_iso = -0.057 %, T_N = 165 K). For x > 0.5 a new P³¹ resonance line is observed, which grows with x at the expense of the previous one. It corresponds to non magnetic layers $\text{S - Ni}{}_{\mathrm{<mtext>2</mtext><mtext>3</mtext>}}\text{(P}{}_2\text{)}{}_{\mathrm{<mtext>1</mtext><mtext>3</mtext>}}\text{- S}$, which progressively replace the paramagnetic ones up to the limit of intercalation x = 1.29. Investigation of the lithium ions mobility through Zeeman and dipolar spin lattice relaxation times T_1～ and T_1D measurements indicates a very low self-diffusion coefficient - D = 10^-13 ? 10^-14cms^-1 -, that is four orders of magnitude smaller than those measured in Li_xTiS₂ compounds. This strongly contrasts with the good electrochemical activity of the Li_xNiPS₃ system.     

Correlation between the atomic and electronic structure of metallic glasses

⁵⁷Fe Mössbauer and photoemission measurements were performed on meltquenched amorphous Fe(Zr, B) and (Fe, Ni)B alloys. The atomic and electronic structure of Fe₉₀Zr₁₀ and Fe₈₈B₁₂ glasses were found to be different. Half of the Zr content could be replaced by B in the Fe₉₀Zr₁₀ glass without changing its structure. Mossbauer investigation of the amorphous (Fe_1?xNi_x)_100?yB_y (0<=x<=0.80, 12<=y<=40) system indicates preferential arrangement of Fe and Ni atoms on the transition metal sites. According to the present XPS measurements there is a remarkable shift of 0.5 eV to higher binding energies of the B ls core level energy in the Ni rich glasses compared to Fe₈₈B₁₂ corresponding to a stronger binding between the Ni and the B atoms than that of Fe and B.     

Deposition of nickel from Ni(CO)4 on palladium and iron surfaces studied by X-ray photoelectron spectroscopy

The interaction of nickel carbonyl, Ni(CO)₄, with evaporated palladium and iron surfaces has been studied at 90 and 290 K by X-ray photoelectron spectroscopy. The carbonyl is weakly adsorbed in molecular form at 90 K on the metals giving a $\text{Ni 2p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ peak at 854.6 eV, a C 1s at 287.2 eV and an O 1s at 533.8 eV. Some fraction of the carbonyl decomposes even at 90 K on iron to give deposited nickel atoms. In the interaction with palladium at 290 K, deposited nickel atoms $\text{(Ni 2p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{= 852.9 eV)}$ and chemisorbed CO are observed. A satellite feature of the $\text{Ni 2p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ peak varies depending on the quantity of the deposited nickel atoms; the main peak-satellite separation increases with increase in the quantity. The same variation is observed for evaporated nickel-palladium alloys. This can be ascribed to the difference in the electronic states of the nickel atoms. The difference is reflected in the reactivity of the atoms with O₂. With iron the deposited nickel atoms show an increase in binding energy of 0.4 eV in the $\text{Ni 2p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ Peak and no satellite when the number of nickel atoms is small. The oxidation of the surface is also studied.     

Structural and electronic properties of PtPd and PtNi nanoalloys

The lowest-energy structures of binary (PtPd)_n, (PtNi)_m, (PtNi₃)_s, and (Pt₃Ni)_s nanoclusters, with n=2–28, m=2–20, and s=4–6, modeled by the many-body Gupta potential, were obtained by using a genetic-symbiotic algorithm. These structures were further relaxed within the density functional theory framework in order to obtain the most stable structures for each composition. Segregation is confirmed in all the (PtPd)_n clusters, where the Pt atoms occupy the cluster core and the Pd atoms are situated on the cluster surface. In contrast, for the (PtNi)_m nanoalloys, the Ni atoms are mainly found in the cluster core and the Pt atoms are segregated to the cluster surface. Likewise, for the (PtNi₃)_s nanoalloys, Ni atoms mainly compose the cluster core but there is no clear segregation of the Pt atoms to the surface. Furthermore, for the (Pt₃Ni)_s bimetallic clusters the Pt atoms concentrate in the cluster core and the Ni atoms are segregated to the surface. On the other hand, it has been experimentally found that the Pt_0.75Ni_0.25 supported nanoparticles present a higher catalytic activity for the selective oxidation of CO in the presence of hydrogen than the Pt_0.5Ni_0.5 and Pt_0.25Ni_0.75 nanoparticles. In order to understand this tendency in the catalytic activity, we also performed density functional calculations of the molecular CO adsorption on bimetallic Pt-Ni nanoclusters with the mentioned compositions.