Sputtering of ordered nickel-aluminium alloys: II. Preferential sputtering of NiAl single crystals and discussion

Atom-probe field-ion microscopy together with X-ray photoelectron spectroscopy and secondary ion mass spectrometry have been applied to the microanalysis of fully ordered NiAl single crystals subjected to 3 keV inert gas ion bombardment. As with the studies of Ni₃Al (the companion paper) aluminium was found to be preferentially sputtered by both argon and xenon bombardment. Comparisons between depth profiles through Ni₃Al and NiAl targets have provided information about the role of binding energies in the selective sputtering process. These data have also permitted conclusions to be drawn about the correct choice of bombarding species for sample cleaning and depth-profiling applications in surface analysis. Examination of field-ion images from specimens after bombardment suggests that the surface is microroughened and this has been confirmed using transmission electron microscopy.     

Stereoelectronic properties of photosynthetic and related systems: Ab initio configuration interaction calculations on the ground and lower excited singlet and triplet states of magnesium chlorin and chlorin

Ab initio configuration interaction wavefunctions and energies are reported for the ground state and many low-lying singlet and triplet states of magnesium chlorin and chlorin, and are employed in an analysis of the electronic absorption spectra of these systems.In chlorin, the calculated visible spectrum consists of two ${}^1\text{(π, π}{}^1\text{)}$ states, the lower energy, y-polarized state exhibiting moderate absorption intensity in contrast to the very weak absorption of the higher energy x-polarized state. The configurational composition of both states is well described by the four-orbital model. Five ${}^1\text{(π, π}{}^1\text{)}$ states are responsible for the Soret band envelope. A moderately intense y-state lies under the low energy edge of the band envelope, while two x-polarized states of moderate and strong intensity, respectively, are responsible for the band maximum. The final two ${}^1\text{(π, π}{}^1\text{)}$ states lie at the high energy edge of the Soret band and introduce a measure of asymmetry into the band envelope. Two ${}^1\text{(n, π}{}^1\text{)}$ states of very weak oscillator strength are also found in this region of the spectrum. All the Soret states are of complex configurational composition, and several of the higher lying states contain contributions from doubly excited configurations.The calculated visible spectrum of magnesium chlorin also consists of two ${}^1\text{(π, π}{}^1\text{)}$ states, with the weakly absorbing x-polarized state lying approximately 200 cm^?1 lower in energy than the moderately intense y-polarized state. The configurational composition of both states is well described by the four-orbital model. Four ${}^1\text{(π, π}{}^1\text{)}$ states constitute the bulk of the intensity in the Soret band envelope. In distinction to chlorin, the moderately intense ${}^1\text{(π, π}{}^1\text{)}$ state at the low energy edge of the band envelope is x-polarized. Two intense ${}^1\text{(π, π}{}^1\text{)}$ states of y- and x-polarization, respectively, constitute the band maximum region, and a single x-polarized state of moderately strong intensity can be assigned to the high energy shoulder of the band envelope. Two other weakly absorbing ${}^1\text{(π, π}{}^1\text{)}$ states are also found in this region, along with another weakly absorbing state of mixed in-plane and out-of-plane polarization. No clearly defined ${}^1\text{(n, π}{}^1\text{)}$ states are observed. As was the case for chlorin, all the Soret states are of complex configurational composition, and some of the higher energy states contain significant contributions from doubly excited configurations.Chlorin and magnesium chlorin both possess three ${}^3\text{(π, π}{}^1\text{)}$ states which lie below S₁ and a single ${}^3\text{(π, π}{}^1\text{)}$ which lies slightly above S₂. All four of the low-lying ${}^3\text{(π, π}{}^1\text{)}$ states in each molecule are well described by the four-orbital model, with T₁ being essentially a single configuration in each case. The remainder of the ${}^3\text{(π, π}{}^1\text{)}$ states are clustered in the same energetic region as the comparable ${}^1\text{(π, π}{}^1\text{)}$ Soret states, with comparably complex configurational compositions.Dipole moments and charge distributions for low-lying singlet and triplet states are also reported, and are used to rationalize chemical reactivity characteristics.     

ESR identification of a new N2− defect in X-ray irradiated NaN3

A relatively weak ESR spectrum is observed in single crystals of NaN₃ after X-ray irradiation at 77 K. This spectrum, which has an anisotropic g value and exhibits a resolved 5-line hyperfine structure with components in the ratio 1:2:3:2:1, corresponds to a single unpaired electron interacting symmetrically with two spin-one nuclei, in three inequivalent sites. The spin-Hamiltonian parameters are: g_x = 2.0054 ± 0.0005, g_y = 2.0045 ± 0.0005, g_z = 1.9688 ± 0.0005, |A_x| = 4.0 ± 0.2 G, |A_y| = 20.0 ± 0.2 G, and |A_z| = 4.9 ± 0.2 G, c-axis, and y is perpendicular to the c-axis. This spectrum, which is clearly different from that of substitutional N₂^?reported by Gelerinter and Silsbee, is attributed to interstitial N₂^?.     

Chemical reactivity and surface-enhanced raman scattering

A mechanism is proposed for surface-enhanced Raman scattering for pyridine which explains the enhancement, the anodizalion “activation”, the significance of silver, the photographitization of coordinated pyridine and formate, the participation of surface roughness, and the irreversibly held yet liquid-like nature of surface pyridine.     

Linear maps that preserve matrices annihilated by a polynomial

Let M_n be the algebra of n×n matrices over an algebraically closed field of characteristic zero. Let f(x) be a polynomial over $\text{F}$ with at least two distinct roots. Then all nonsingular linear maps L:M_n→M_n that map matrix roots of F(x)=0 into matrix roots of f(x}=0 are found.     

AB initio calculations of the electronic properties of N4− in KN3

The energies of the ground state and low-lying excited states of the N₄^? defect in KN₃ have been calculated using ab initio techniques. A rectangular equilibrium geometry with dimensions X = 2.76 and Z = 2.47 a.u. and ground state symmetry of Γ₄⁺ was determined by calculating N₄^? as a free radical. For this ground state the unpaired electron is in a π orbital which is consistent with the experimental hyperfine tensor only if one edge of the N₄^? radical is parallel to the c axis in KN₃. These results were used to calculate the X²Γ₄⁺ state of N₄^? in the crystal field of KN₃, yielding an energy of ?217.899 Hartrees. The isotropic hyperfine constant was calculated to be a = 2.1 G and the components of the anisotropic hyperfine tensor as B_xx = ?3.4 G, B_yy = 7.0 G and B_zz = ?3.6 G, in good agreement with experimental and INDO results. Several excited states were calculated for the N₄^? defect in KN₃. When an estimate was made of the correlation energy, the transition energy of the X²Γ₄⁺→A²Γ₃^? transition agreed well with the peak energy of the 780 nm absorption band which has been attributed to N₄^?.     

Uniqueness of the inversive plane of order 7

A search has shown that any inversive plane of order 7 must be isomorphic with the Miquelian plane. The method used was explicitly set out in a companion paper, which was concerned with a plane of order 5.     

Linear relativistic hamiltonians

A 2(2J + 1)-component relativistic Hamiltonian H that describes free particles of mass m and spin J is said to be linear if it has the form $\text{H = h}\text{x}\text{?}\text{·}\text{p}\text{+ gm}$, where $\text{x}\text{\_.}\text{= i[H,}\text{x}\text{]}{}_{\mathrm{?}}$, h is a numerical factor, and g commutes with x and p. All such Hamiltonians are found, provided that the metric is either the unit matrix or ?₃ and provided that the theory is invariant under the discrete symmetries. If the operator Γ in the generator $\text{K}\text{=}\text{1}\text{2}\text{[}\text{x}\text{, H]}{}_{\mathrm{+}}\text{+ Γ}$ of Lorentz boosts is required to be local, there are only two possibilities; either Γ = 0, which generalizes the Dirac spin-$\text{1}\text{2}$ theory, or $\text{Γ = ??}{}_3\text{(}\text{1}\text{2m}\text{)}\text{S × p}$, which generalizes the Sakata-Taketani spin-0 and spin-1 theories. The relationship to linear manifestly covariant equations and its significance is discussed.