Electronic structure and bonding of cobalt monoxide, CoO, and its ions CoO+ and CoO-: an ab initio study

We present a systematic and high-level ab initio study of CoO and its ions, CoO(+) and CoO(-). Employing variational multireference (MRCI) and single-reference coupled-cluster methods combined with basis sets of quintuple quality, we have calculated 50, 31, and 7 bound states for CoO, CoO(+), and CoO(-), respectively. For all these states, complete potential energy curves have been constructed at the MRCI level of theory, whereas for a few low-lying states core subvalence and scalar relativistic effects have been taken into account. We report energetics, spectroscopic parameters, dipole moments, and spin-orbit coupling constants. The ground states of CoO, CoO(+), and CoO(-) are X(4)Δ, X(5)Δ, and X(5)Δ, respectively, the latter established for the first time. The CoO is quite ionic with a Co to O Mulliken charge transfer of ~0.6 electrons and a dipole moment μ(X(4)Δ) = 4.5 ± 0.1 D. The overall agreement between theory and experiment is good, but there are also important deviations. Despite the seeming simplicity of these diatomic species, reliable results can only be obtained at a high level of theory.     

Tracer-diffusion of Zn2+ ions in cobalt sulphate

Tracer-diffusion of Zn²⁺ ions in the presence of CoSO₄ is studied at 25°C in 1% agar gel over a concentration range of 10^–5 to 0.25M using a zone-diffusion technique. The deviations observed between experimental and theoretical values of diffusion coefficients are explained by considering different types of interactions occurring in the ion-gel-water system. Further, study of the obstruction, effect in the diffusion of Zn²⁺ ions at different concentrations of CoSO₄ reveals that the -value decreases with increasing concentration of the electrolyte. This observation is accounted on the basis of competitive hydration between ions and agar molecules.     

First principles study of magnetism in nanographenes

Magnetism in nanographenes [also known as polycyclic aromatic hydrocarbons (PAHs)] is studied with first principles density functional calculations. We find that an antiferromagnetic (AFM) phase appears as the PAH reaches a certain size. This AFM phase in PAHs has the same origin as the one in infinitely long zigzag-edged graphene nanoribbons, namely, from the localized electronic state at the zigzag edge. The smallest PAH still having an AFM ground state is identified. With increased length of the zigzag edge, PAHs approach an infinitely long ribbon in terms of (1) the energetic ordering and difference among the AFM, ferromagnetic, and nonmagnetic phases and (2) the average local magnetic moment at the zigzag edges. These PAHs serve as ideal targets for chemical synthesis of nanographenes that possess magnetic properties. Moreover, our calculations support the interpretation that experimentally observed magnetism in activated carbon fibers originates from the zigzag edges of the nanographenes.     

First principles study of photostability within hydrogen-bonded amino acids

The photochemistry and photophysics of a two-glycine minimal model is studied at the CASPT2//CASSCF level of theory. Different photoinduced processes are discussed, on the basis of the calculated minimum energy paths and the characterization of the electronic state crossings. Two main processes could provide UV-photostability to the hydrogen-bonded peptide system: (i) forward-backward photoinduced electron/proton transfer involving the H in the hydrogen bond, (ii) singlet-singlet energy transfer between two amino acids, providing ultrafast population of the low-energy n,π* state.     

First principles investigation of the electronic structure of the iron carbide cation, FeC+

We have studied 40 states of the diatomic iron carbide cation FeC(+) by multireference methods coupled with relatively large basis sets. For most of the states, we have constructed complete potential energy curves, reporting dissociation energies, usual spectroscopic parameters, and bonding mechanisms for the lowest of the studied states. The ground state is of (2)Delta symmetry, with the first excited state (a(4)Sigma(-)) lying 18 kcal/mol higher. The X(2)Delta state displays a triple-bond character, with an estimated D(0) value of 104 kcal/mol with respect to the adiabatic products or 87 kcal/mol with respect to the ground-state fragments.     

Sorption of nickel and cobalt ions onto cobalt and nickel ferrites

The corrosion of the metal parts in the primary circuit of pressurized water reactors leads to the release of colloidal particles (NiFe(2)O(4), CoFe(2)O(4), NiO, Ni...) and ionic species (Co, Ni, Cr...). Particles can interact with ionic species in the primary medium, contributing to their transport and to their deposition onto surfaces outside the neutron flux generating radioactive contamination. Sorption and zetametry experiments at 25 °C were performed on the Ni(2+)/CoFe(2)O(4) and Co(2+)/NiFe(2)O(4) systems in order to determine the behaviour of corrosion products in the fluid of the primary circuit. Sorption appears as surface complexation starting from pH 6 and is followed by precipitation of hydroxide above pH 7.5. Complexation and solubility constants were obtained from the modelling of sorption curves. The two oxide systems present a very similar sorption behaviour, but some differences, due to their different isoelectric points, could be observed on zetametric measurements.     

First principles investigation of chromium carbide, CrC

We have investigated the electronic structure of 14 states of the experimentally unknown diatomic molecule chromium carbide, CrC, using standard multireference configuration interaction methods and high quality basis sets. We report potential curves, binding energies, and a number of spectroscopic parameters. The ground state of CrC, X 3Sigma-, displays triple-bond character with a binding energy of D(e)=89 kcal/mol and an internuclear separation of r(e)=1.63 A. The first excited state (1 5Sigma-) lies 9.2 kcal/mol higher. All the states studied are fairly ionic, featuring an electron transfer of 0.3-0.5e- from the metal atom to the carbon atom.     

First principles molecular dynamics study of filled ice hydrogen hydrate

We investigated structural changes, phase diagram, and vibrational properties of hydrogen hydrate in filled-ice phase C(2) by using first principles molecular dynamics simulation. It was found that the experimentally reported "cubic" structure is unstable at low temperature and∕or high pressure: The "cubic" structure reflects the symmetry at high (room) temperature where the hydrogen bond network is disordered and the hydrogen molecules are orientationally disordered due to thermal rotation. In this sense, the "cubic" symmetry would definitely be lowered at low temperature where the hydrogen bond network and the hydrogen molecules are expected to be ordered. At room temperature and below 30 GPa, it is the thermal effects that play an essential role in stabilizing the structure in "cubic" symmetry. Above 60 GPa, the hydrogen bonds in the framework would be symmetrized and the hydrogen bond order-disorder transition would disappear. These results also suggest the phase behavior of other filled-ice hydrates. In the case of rare gas hydrate, there would be no guest molecules' rotation-nonrotation transition since the guest molecules keep their spherical symmetry at any temperature. On the contrary methane hydrate MH-III would show complex transitions due to the lower symmetry of the guest molecule. These results would encourage further experimental studies, especially nuclear magnetic resonance spectroscopy and neutron scattering, on the phases of filled-ice hydrates at high pressures and∕or low temperatures.     

Theoretical study of the structurally nonrigid ions LiP 2 + , HP 2 + , and H3P 2 +

New Chemical Problems Institute, USSR Academy of Sciences. Translated from Zhurnal Strukturnoi Khimii, Vol. 30, No. 4, pp. 164–167, July–August, 1989.     

Efficient electrocatalytic hydrogen production from H+ ions using specially designed boron-capped cobalt clathrochelates

Specially designed hexachlorine-containing cobalt(II) tris-dioximate clathrochelates were found to efficiently electrocatalyze the production of molecular hydrogen from H(+) ions without the overpotential of this process.     

First principles study of the reaction of formic and acetic acids with hydroxyl radicals

The oxidation of formic and acetic acids with hydroxyl radicals was studied as a model for the oxidation of larger carboxylic acids using first principles calculations. For formic acid, the CBS-QB3 activation barriers of 14.1 and 12.4 kJ/mol for the acid and for the formyl channel, respectively, are within 3 kJ/mol of benchmark W1U values. Tunneling significantly enhances the rate coefficient for the acid channel and is responsible for the dominance of the acid channel at 298 K. At 298 K, tunneling correction factors of 339 and 2.0 were calculated for the acid and the formyl channel using the small-curvature tunneling method and the CBS-QB3 potential energy surface. The Wigner, Eckart, and zero-curvature tunneling methods severely underestimate the importance of tunneling for the acid channel. The resulting reaction rate coefficient of 0.98 x 10(5) m(3)/(mol x s) at 298 K is within a factor 2-3 of experimental values. For acetic acid, an activation barrier of 11.0 kJ/mol and a tunneling correction factor of 199 were calculated for the acid channel. Two mechanisms compete for hydrogen abstraction at the methyl group, with activation barriers of 11.9 and 12.5 kJ/mol and tunneling correction factors of 9.1 and 4.1 at 298 K. The resulting rate coefficient of 1.2 x 10(5) m(3)/(mol x s) at 298 K and branching ratio of 94% compare well with experimental data.     

First principles and experimental 1H NMR signatures of solvated ions: The case of HCl(aq).

A combined experimental and ab initio study is presented of the 1H NMR chemical shift distribution of aqueous hydrogen chloride solution as a function of acid concentration, based on Car-Parrinello molecular dynamics simulations and fully periodic NMR chemical-shift calculations. The agreement of computed and experimental spectra is very good. From first-principles calculations, we can show that the individual contributions of Eigen and Zundel ions, regular water molecules, and the chlorine solvation shell to the NMR line are very distinct and almost independent of the acid concentration. From the computed instantaneous NMR distributions, it is further possible to characterize the average variation in hydrogen-bond strength of the different complexes.     

The separation of cobalt,manganese and sodium by electrophoretic focussing of ions

Electrophoretic focussing of cobalt(II), manganese(Il) and sodium(I) ions was investigated with EDTA as a complexing agent. Excellent separations of binary mixtures Co/Mn and Mn/Na are described, even for very unfavourable activity ratios. Separation of Co/Mn/Na is only satisfactory if the activities are of the same order of magnitude.     

First principles study of adsorption and dissociation of CO on W(111)

The adsorption and dissociation of carbon monoxide on the W(111) surface is studied with density functional theory. The CO molecule is found to adsorb in end-on configurations (alpha states) and inclined configurations (beta states). The dissociation of the most strongly bound beta state CO is found to have an activation energy of about 0.8 eV, which is lower than the energy required to desorb CO molecularly from the surface. The diffusion of CO and O on W(111) is predicted to be facile at room temperature, whereas C atoms are virtually immobile up to approximately 600 K, according to our calculations. Preadsorbed carbon atoms are shown to prevent the dissociation of CO by blocking the most strongly bound beta state adsorption site and by blocking the dissociation pathway. We predict that dissociation of CO on W(111) is a self-poisoning process.     

First principles study of the ground and excited states of FeO, FeO+, and FeO(-)

Through a variety of highly correlated methods combined with large basis sets we have studied the electronic structure of FeO, FeO(+), and FeO(-). In particular, we have constructed complete potential energy curves for 48, 24, and 4 states for the FeO, FeO(+), and FeO(-) species, respectively, at the multireference level of theory. For all states examined we report energetics, common spectroscopic parameters, and dipole moments. Overall our results are in good agreement with experiment, but we have encountered as well interesting differences between experiment and theory deserving further investigation.     

Simple and mixed complexes of cobalt(II) and cobalt(III) ions

Summary Bivalent and trivalent cobalt complexes with 1-(2-pyridylazo)-2-naphthol (PAN), PAN+1, 10-phenanthroline and PAN+2, 2-bipyridyl were prepared and characterized by physico-chemical and magnetic measurements. The spectral studies suggest that PAN behaves as a bidentate ligand and is coordinated to metal ions through oxygen and (pyridine) nitrogen, whereas 1, 10-phenanthroline and 2, 2-bipyridyl are coordinated through (pyridine) nitrogen. The tentative (M–O) and (M–N) band assignments in the lower i.r. region, and magnetic moment data favour four coordination for the complexes studied.     

UV-visible spectroscopic study of the salicyladehyde benzoylhydrazone and its cobalt complexes

Salicyladehyde benzoylhydrazone (SBH) has three groups suitable for forming coordination bond with transition metal. The UV-vis absorption spectra of SBH and its Co(II) complexes in various media were studied by using the deconvolution method. It is found that the structure of complex in solution is different from those in solid crystals. The nature of complexes in solution depends on acidity of the phenolic proton of SBH and on the medium. In neutral or slightly acid medium, the SBH is a non-charged bidentate ligand. And the "free" hydroxyl group on the SBH molecule makes it possible to form hydrogen bonds in solution. In basic medium, the SBH is a mono, negatively charged tridentates ligand.     

First principles calculations on structure, bonding, and vibrational frequencies of SiP2

Pyrite type SiP(2) is reinvestigated by first principles calculations on various levels of functionals including local density approximation, generalized gradient approximation, Becke-Lee-Yang-Parr hybrid functional, and the Hartree-Fock method. SiP(2) is seen as a model compound with molecular [P-P] entities and [SiP(6)] octahedra. Structure and bonding are addressed by electronic structure calculations. Special attention is spent on P-P and Si-P bonds in terms of bond lengths and respective stretching modes from simulated Raman spectra. The electronic structure is analyzed in both direct and momentum space by the electron localization function and site projected density of states. The main goals of this work are to understand the nature of chemical bonding in SiP(2) and to compare and contrast the different methods of calculation.