Ab initio potential curves for the lowest 1Σ+ and 3Π states of the ion CN+

Ab initio configuration-interaction calculations using a 9s5p|3s2p gaussian basis supplemented with polarization functions are presented for potential curves for the a ¹Σ⁺ and the lowest ³Π state of CN⁺. The two states are very close in energy and calculations at this level do not give an unequivocal indication of the identity of the ground state.     

Predissociation of the C2Σu+ state of N2+

Two mechanisms for the predissociation of the C²Σ_u⁺ state of N₂⁺ are discussed - the accidental mechanism and a direct, homogeneous process C → B²Σ_u⁺. The matrix elements for the latter channel are dominated by a contribution from the nuclear kinetic energy operator, containing a Franck-Condon integral of form 〈?|?/?R|υ′〉.     

The lowest states of the O3+ ion

A CAS SCF calculation of the potential surfaces for the lowest states of the O₃⁺ ion is reported. An assignment of the bands in the HeI photoelectron spectrum is based upon calculated vibration profiles. This assignment shows the ground state of the ion to have ²B₂ symmetry. Also the weak bands at 15.6, 16.5 and 17.5 eV are reassigned.     

Vibration-rotation spectroscopy of the HD+ ion

A new method of detecting vibration-rotation transitions in HD⁺ is described. The ion-beam laser-resonance method employs Doppler tuning and relies upon the detection of infrared photodissociation of levels close to the dissociation limit of HD⁺. Measurements of nine rotational components of the v = 18 ? 16 band are described. A review of the theoretical methods for the calculation of energy levels in HD⁺ is given, followed by a comparison of the experimental results with the best available theoretical values. The resolution of structure arising from proton hyperfine interaction is also described.     

AB initio study of the HN2+ molecule ion and its dissociation products in ground and excited states

Non-empirical SCF and Cl calculations for the HN₂⁺ molecule ion are reported. Potential curves for ground and excited states of this system are obtained, with particular emphasis on the manner in which these species dissociate upon NH stretch. The electronic spectrum of HN₂⁺ is also calculated and compared with that of an unperturbed N₂ molecule.     

The photodissociation of CH+ through absorption into the A1Π state

Cross sections for the photodissociation of ground state CH⁺ ions through absorption into the A¹Π state are calculated for the lowest three vibrational levels. At threshold the cross sections for υ″ = 0, 1 and 2 are respectively 5.0 × 10^?20 cm², 8.1 × 10^?19 cm² and 2.6 × 10^?18 cm².     

Laser-induced fluorescence of CsH: The X1Σ+ state dissociation energy

Laser-induced fluorescence of CsH from the A¹Σ⁺ electronic state to the X¹Σ⁺ state was recorded using high-resolution Fourier transform spectrometry. Ground-state vibrational levels were observed from ν″ = 1 to the dissociation limit. These measurements showed anomalies in the X¹Σ⁺ potential energy curve due to the avoided crossing of ionic and covalent potential curves. Accurate molecular constants were derived for the lower X¹Σ⁺ vibrational levels. The observation of a quasibound level gave the first experimental determination of the dissociation energy (in cm^?1): 14802 ? D_c ? 14813.     

Shape resonances of the A1Π state of CH+

Potential curves for the CH⁺ X¹Σ⁺ and A ¹Π states are constructed using the best experimental and theoretical information. The A ¹Π curve is used to calculate the locations and widths of rotationally quasi-bound levels. Oscillator strengths from v'' = 0 of the X state to the shape resonances are also calculated. The results are in good agreement with experiment.     

Dynamics of ion—molecule processes: A crossed-beam study of the reaction B+(3P) + H2 → BH+ + H

Dynamics of the reaction B⁺(³P) + H₂ → BH⁺ + H has been studied in crossed-beam scattering experiments in the collision-energy range 0.6–2.3 eV (c.m.). Scattering diagrams obtained show that in the reaction both the ground state BH⁺(²Σ⁺) and the excited state BH⁺(² Π) (if energetically accessible) are formed; both states are formed via intermediate complexes whose mean lifetimes are of the order of 10^?13 s and decrease with increasing collision energy, as reflected in the decreasing forward-backward symmetry of the scattering diagrams.     

The structure of the H3O+ (hydronium) ion

Near Hartree-Fock level ab initio molecular orbital calculations on H₃O⁺ and a minimum energy structure with θ(HOH) = 112.5° and r(OH) = 0.963 Å and an inversion barrier of 1.9 kcal/mole. By comparing these results to calculations on NH₃ and H₂O, where precise experimental geometries are known, we estimate the “true” geometry of isolated H₃O⁺ to have a structure with θ(HOH) = 110-112°, r(OH) = 0.97–0.98 Å and an inversion barrier of 2–3 kcal/mole. Our prediction for the proton affinity of water is ≈ 170 kcal/mole, which is somewhat smaller than the currently accepted value.     

The sodium hyperfine splitting constant for the Na+Furil⨪Na+ triple ion

The small magnitude and positive sign of the sodium atom hyperfine splitting constant of the Na⁺furil^? radical triple ion is interpreted by elementary MO arguments. The model gives some insight into the nature of the Na—O coordination in such species.     

Jahn-Teller distortion in the SnH4+ ion

The extension of the Jahn-Teller distortion of the SnH₄⁺ structure is estimated from ab initio SCF CI calculations using pseudopotential atomic approximation with and without relativistic correction. These calculations show the lowest minima of SnH₄⁺ to have C_2v symmetry and are very close to the C_3v minima. The calculated photoelectron spectrum of SnH₄ is in good agreement with the experimental values.     

The pair polarizabilities of Li+/Li+ and Cl−/Cl−

Ab initio SCF MO energies and pair polarizabilities are reported for the pairs Li⁺/Li⁺ and Cl^?/Cl^? over the ranges of internuclear separation which are of importance in molten LiCl. The shapes of the β(R) curves resemble those of inert gas diatoms. The Cl^?/Cl^? interaction is predicted to make a rather small contribution to those properties of molten LiCl which depend on $\text{α}$⁽²⁾(R), and a larger contribution to properties which depend on β(R). The Li⁺/Li⁺ interaction contributes almost nothing to the bulk polarizability.     

Measurement of the product ion ratio N4+/N3+ in the radiolysis of nitrogen

The ratio of N₄⁺ to N₃⁺ formed in the radiolysis of gaseous nitrogen has been measured to be 4.7 ± 0.4 using a time-resolved atmospheric pressure ionization mass spectrometer. The limit of error has been evaluated from the ion mass discrimination of the apparatus.     

Solvent extraction of H3O+, NH4+, Ag+, K+, Rb+ and Tl+ into nitrobenzene by using cesium dicarbollylcobaltate in the presence of a hexaarylbenzene-based receptor

From extraction experiments and γ-activity measurements, the extraction constants corresponding to the general equilibrium M⁺(aq) + 1·Cs⁺(nb) \rightleftarrows \rightleftarrows 1·M⁺(nb) + Cs⁺(aq) taking part in the two-phase water–nitrobenzene system (1 = hexaarylbenzene-based receptor; M⁺ = H₃O⁺, NH₄ ⁺, Ag⁺, K⁺, Rb⁺, Tl⁺; aq = aqueous phase, nb = nitrobenzene phase) were evaluated. Furthermore, the stability constants of the ML⁺ complex species in nitrobenzene saturated with water were calculated; they were found to increase in the series of Rb⁺ < K⁺ < Ag⁺, Tl⁺ < H₃O⁺, NH₄ ⁺.     

Some ab initio calculations related to the predissociation of the C2Σu+ state of N2+

Ab initio calculations in the “first-order wavefunction” CI approximation have been performed for several states of N₂⁺ with ²Σ_u⁺, ²Σ_u^?, ⁴Π_u symmetry. A calculation of the electronic factor of the vibronic interaction between the B²Σ_u⁺ and C²Σ_u⁺ states seems to support the suggestion of Tellinghuisen and Albritton that the C state is predissociated by the continuum of the B state through nuclear momentum coupling.     

The properties of clusters in the gas phase: ammonia about Bi+, Rb+, and K+

Thermodynamic data are reported for NH₃ clustered about Bi⁺, Rb⁺, and K⁺ in the gas phase. Unusually strong bondings of NH₃ to Bi⁺ suggests the probable importance of partial covalent bonding in stabilizing the first ligand cluster. Differences in relative bond strengths for NH₃ and H₂O about Rb⁺ andK⁺ are consistent with the results of extended Hückel calculations reported herein.     

Revised theoretical energy for the a 3Σg+ state of H2

The Born—Oppenheimer energy of H₂ in the a ³Σ_g⁺ state has been improved. The new result, with estimated values of the relativistic and nonadiabatic corrections, and with the previously computed adiabatic corrections yields T₀ = 95077.3 cm^?1 in a good agreement with the recent experimental value T₀ = 95076.4 ± 0.5 cm^?1 of Miller and Freund.     

Sensitization of Tb3+ luminescence with Ce3+ in LaOBr: Tb3+, Ce3+

Luminescence emission and uv-excitation properties of LaOBr: Tb³⁺, LaOBr: Ce³⁺, and LaOBr: Tb³⁺, Ce³⁺ phosphors were studied. The visible emission spectra of La_0.995Tb_0.005OBr consists of⁵D_3,4 →⁷F_3–6 transitions in the wavelength range of 410–630 nm. The excitation of the Tb³⁺ ion gives a broad 4f → 5d transition band at 254 nm and weaker4f → 4f transition lines above 300 nm. The uv-excitation and emission of La_0.995Ce_0.005OBr at 290, 315, 355 (excitation), and 440 nm (emission) originate from transitions between the 4f-ground state and the four crystal field components of the5d²D excited state. The sensitization of Tb³⁺ luminescence in LaOBr with Ce³⁺ at varying concentrations is described and discussed. With increasing Ce³⁺ concentration the ⁵D₃ →⁷F transitions of Tb³⁺ quench totally and the⁵D₄ →⁷F transitions begin to quench gradually. The excitation spectrum of the⁵D₄ →⁷F₅ transition of Tb³⁺ consists of four bands due to Tb³⁺ and Ce³⁺, of which the three Ce³⁺ bands increase in intensity and the Tb³⁺ band decreases as the Ce³⁺ concentration is increased.     

A pios study of the reaction Ne(3P2,0) + HCl → Ne + HCl+ (A2Σ+) + e−

The HCl⁺ (A) vibrational state distributions from the title reaction were studied over the 48–110 meV collision energy range. The $\text{1}\text{0}$ and $\text{2}\text{0}$ ratios increase by factors of about 1.3 and 2.5, respectively. The branching ratios appear to be determined primarily by Franck-Condon factors, and by the endoergicity of the ν′ = 2 level.