Nature of metal-nonmetal transition in metal-ammonia solutions. II. From uniform metallic state to inhomogeneous electronic microstructure

Applying semianalytical models of nonideal plasma, we evaluate the behavior of the metallic phase in metal-ammonia solutions (MAS). This behavior is mainly controlled by the degenerate electron gas, which remains stable down to 5 MPM due to high solvent polarizability and strong dielectric screening of solvated ions. Comparing the behavior of the metallic state with those of localized solvated electrons, we have estimated the miscibility gap Delta n for various alkali metals and found Delta n(Na)>Delta n(K). It is rather narrow in Rb-NH3 and does not occur in Cs-NH3 solutions, which is in full agreement with the experiments. The case of Li is discussed separately. The difference calculated in the excess free energies of the metallic and nonmetallic phases is in the order of kBT, yielding a thermally fluctuating mixed state at intermediate metal concentrations. It results in a continuous metal-nonmetal (MNM) transition above the consolute point Tc and a phase separation below Tc. We propose a criterion for the MNM transition which may be attributed to the line of the maximum of compressibility above Tc. This line crosses the spinodal one at the critical temperature. Finally, we assert that a new electronic phase similar to microemulsion should also arise between the spinodal and the binodal lines.     

A dielectric anomaly at the metal-nonmetal transition

The divergence in the real part of the dielectric constant which accompanies a metal-nonmetal transition is described. Particular attention is paid to metal-ammonia solutions.     

Taylor dispersion measurements at low electrolyte concentrations. I. Tetraalkylammonium perchlorate aqueous solutions

An equipment for the determination of mutual diffusion coefficients using the Taylor's dispersion technique is described. The radius of the capillary was determined with the help of various calibration methods. Diffusion coefficients of aqueous tetraalkylammonium perchlorates, Me₄NClO₄, and Et₄NClO₄, were measured at 25°C in the concentration range 10^–3 to 5×10^–2 mol-dm^–3, and the slightly soluble Pr₄NClO₄ up to 1×10^–2 mol-dm^–3. The slope of linear plots ofD vs. is in agreement with theory, in contrast to the limiting valuesD ₀, which all deviate by about –5% from the Nernst-Hartley values.     

Solvated electrons at the water-air interface: surface versus bulk signal in low kinetic energy photoelectron spectroscopy

Time-resolved photoelectron spectroscopy at low kinetic energies (?5 eV) is applied to dilute iodide solutions with different surface and bulk contributions. The results indicate a pronounced surface sensitivity. Signals assigned to solvated electrons near the liquid surface decay rapidly on a sub-ps timescale. In contrast to the literature, a long-lived surface solvated electron at 1.6 eV binding energy is not observed.     

Studies on the viscosity behavior of polymer solutions at low concentrations

Viscosity measurements had been made on poly(vinyl alcohol) (PVA), poly(N-vinyl-2-pyrrolidone) (PVP) and poly(ethylene oxide) (PEO) solutions down to low concentrations. It was found that defined as the flow time of the pure solvent in ideal conditions and obtained practically by extrapolating the flow time of polymer solution t to zero concentration, was not equal to the flow time of the pure solvent t₀ measured. The reduced viscosity η_sp/C determined by (t/t₀-1)/C exhibited either a drastic increase or a significant decrease with dilution, depending upon the polymer solution investigated. On the other hand, η_sp/C determined by was proportional to C even at low concentrations. The anomalous viscosity behavior of neutral polymer solutions at low concentrations, therefore, was due to the incorrect method by which η_sp/C was determined. The detailed experiments indicated that the effective diameter of the viscometer capillary, the surface property of the capillary wall and the additional pressure corresponding to the measurement of t and t₀ for PVA, PVP and PEO solutions were not the same. Taking into account the contact anger and the surface tension of the liquid, together with the geometric parameter of the viscometer, the influence of the additional pressure upon the flow time measurement could be studied quantitatively. The calculation was in a good agreement with the experimental result. According to the method presented in this paper, the thickness of the adsorbed polymer layers on the capillary walls could be determined. It was noted that the thickness of the adsorbed polymer layers on the capillary walls was closely related to the solvent in which the polymer molecules were dissolved. The polymer molecular weight, however, had little or no effect on the thickness of the adsorbed polymer layers on the walls of the viscometer capillary.     

Solvated electrons at elevated temperatures in different alcohols: Temperature and molecular structure effects

The absorption spectra of solvated electrons in pentanol, hexanol and octanol are measured from 22 to 200, 22 to 175 and 50 to150 °C, respectively, at a fixed pressure of 15 MPa, using nanosecond pulse radiolysis technique. The results show that the peak positions of the absorption spectra have a red-shift (shift to longer wavelengths) as temperature increases, similar to water and other alcohols. Including the above mentioned data, a compilation of currently available experimental data on the energy of absorption maximum (E_max) of solvated electrons changed with temperature in monohydric alcohols, diols and triol is presented. E_max of solvated electron is larger in those alcohols that have more OH groups at all the temperatures. The molecular structure effect, including OH numbers, OH position and carbon chain length, is investigated. For the primary alcohols with same OH group number and position, the temperature coefficient increases with increase in chain length. For the alcohols with same chain length and OH numbers, temperature coefficient is larger for the symmetric alcohols than the asymmetric ones.     

Infrared spectroscopy of aqueous ionic salt solutions at low concentrations

The analysis by infrared spectroscopy of aqueous solutions of the binary inorganic salts NaI and NaCl and the ternary salts CaCl2 and BaCl2 at concentrations from 1000 to 2 mM was carried out to complement a previous study done at higher concentrations on nine binary salts (alkali halides) and one ternary salt (MgCl2) [J.-J. Max and C. Chapados, J. Chem. Phys. 115, 2664 (2001)]. These salts are completely ionized in aqueous solutions, forming monoatomic species that do not absorb IR but that perturb the surrounding water, modifying its spectrum. The factor analysis of the spectra revealed that all these salt solutions were composed of two water types: pure water and salt solvated water. The authors obtained pure salt solvated water spectra for all the salts using an extrapolation technique. The water types obtained are constant for the binary and ternary salts down to 2 mM. For the binary salts, we determine that 5.0 and 4.0 water molecules are solvated to the Na+-Cl- and Na+-I- ion pairs, respectively. These numbers are the same as that obtained at higher concentrations. For the new ternary salts, we find that 6.0 and 8.0 water molecules are solvated to Ca++-(Cl-)2 and Ba++-(Cl-)2 ion pairs, respectively. These numbers are higher than the four water molecules solvated to Mg++-(Cl-)2 ion pairs determined previously, but show a progression that follows their atomic numbers. These results constitute new experimental results on "simple" systems whose molecular organization is still a matter of debate. The IR method that probes the system at the molecular level is a method different than the macroscopic ones that give the activity coefficients. The IR gives direct observation at the molecular level of the strong ion-water interactions that are often neglected and its water structure not considered in macroscopic methods. The present results and their analysis together with those obtained by other methods will facilitate the determination of the organization of these aqueous systems.     

Aqueous solutions of transition metal containing micelles

Incorporation of d- or f-block metals into ligand systems that renders a metal complex surface-active or drives its partitioning into surfactant phases enables the localisation of chemical functionality at interfaces. This article discusses a number of fundamental aspects of these interesting materials and examines potential applications.     

Resonance Raman spectra of n-pi* singlet-triplet transition of p-benzoquinone at low concentrations

A weak visible absorption spectrum of p-benzoquinone (p-BQ) in CS2 due to n-pi* singlet-triplet transition was measured. Using the resonance Raman (RR) effect in liquid-core optical fiber (LCOF), we have obtained the 514.5 nm excited RR spectra of p-benzoquinone near 1445 cm(-1) and have demonstrated that the new characteristic RR band is attributed to the symmetric C=O stretch (nu(C=O)) of n-pi* singlet-triplet transition of p-BQ. The effect of solution concentration on the RR band was investigated at very low concentrations. The RR peak spreads toward short wavelength side with decreasing solution concentration ranging from 10(-7) to 10(-11) mol L(-1), whereas the blue-shift isn't obvious when the concentration is, at single molecule level, lower than 10(-11) mol L(-1). Our result is useful for single molecule detection to some extent.     

Modeling of gamma-ray radiolysis data at moderate and low solute concentrations in aqueous solutions

A radiation chemical model developed for use in pulse radiolysis studies employing high energy electrons has been applied to the calculation of yields in aqueous chemical systems irradiated with ⁶⁰Co γ-rays. The fit between model calculations and experimental data is almost within experimental error in most instances. Trends are accurately predicted where quantitative agreement is not found. Predictions of molecular yields of H₂ and H₂O₂ in the presence of scavengers of precursors of these molecules are in good agreement if an initial molecular yield is assumed for both molecules. Agreement between model predictions and experimental data is reasonable at low solute concentrations where back reactions of spur intermediates are important. The model appears to be useful in modeling steady state γ radiolysis as well as pulse radiolysis data. Implications of the model in predicting possible errors in rate constant determinations are discussed.     

On the role of d electrons in chemisorption and catalysis on transition metal surfaces

A new model is proposed for the role of the d electrons in chemisorption and catalysis on transition metal surfaces. In this model, the d electrons remain localized on the atoms and do not participate in forming dsp hybrid bonds with the adsorbate. However, electrons in doubly-occupied d orbitals can be promoted to anti-bonding or non-bonding valence orbitals. These additional electronic configurations help increase the binding energy of the adsorbate and help stabilize reaction intermediates. This effect is enhanced by spatial rotation of the singly-occupied d orbitals which become perpendicular to the adsorbate. The singly-occupied d orbitals are also able to recouple their spins during the reaction, allowing the reaction to proceed on otherwise forbidden reaction paths.     

Measurement of the dielectric relaxation property of water-ion loose complex in aqueous solutions of salt at low concentrations

Electrolytes and their dissociated ions are thought to form positive or negative hydration layers around them. In this study, we have developed a method to determine the volume and the dielectric relaxation property (relaxation frequency f c, dispersion intensity delta) of the water hydrating ions in salt solutions. The method consists of four steps: (1) By use of a high-resolution microwave dielectric spectroscopy technique, the dielectric spectra of sample salt solution and bulk water are measured in pair. (2) The dielectric spectrum of solutes (ions) with water layers for a given volume fraction varphi is then calculated from each pair of dielectric spectra of a sample salt solution and reference water according to the Hanai mixture theory. (3) Each spectrum of solutes with water layers at a given varphi is decomposed into a few Debye relaxation functions and the bulk water component. (4) The volume fraction varphi is operationally decreased from 0.5, and steps (2) and (3) are repeated at each varphi until the bulk water component vanished. Then the volume fraction of the hydrated solutes (ions) in solution is determined. The method was applied to NaF and NaCl solutions. As a result the different spectral intensity was nearly proportional to the salt concentration below 0.2 M in the frequency range of 3-26 GHz. The hydration number N h and the dielectric relaxation property of the hydration layer for each salt solution was successfully determined as ( f c1, delta 1, N h)= (18.7, 44.9, 27.9) for NaCl and ( f c1, delta 1, f c2, delta 2, N h) = (26.0, 6.70, 5.64, 19.2) for NaF.     

Single-molecule precipitation of transition metal(I) chlorides in water clusters.

Metal ions in unusual oxidation states can be introduced into water clusters using a standard laser vaporization source. Such nanosolutions of a single ion in typically 50 water molecules are comparable to a 1 M bulk solution, and their chemistry can be studied in the ion trap of a Fourier transform ion cyclotron resonance mass spectrometer. We find that a strong acid like hydrogen chloride oxidizes the early transition metal vanadium to the more common +III state, while later first row transition metals retain their unusual +I oxidation state, and the binary metal chlorides M(I)Cl precipitate.     

Spreading of surfactant solutions over thin aqueous layers at low concentrations: Influence of solubility

A small droplet of aqueous surfactant solution at concentration below CMC was deposited on a thin water layer. A moving circular wave in the centre was formed. The time evolution of the radius of the wave was monitored. Two surfactants of different solubility were used. It was shown that the time evolution of the moving front (i) proceeds in two stages: a fast first stage and slower second stage; (ii) the time evolution of the front motion substantially depends on the surfactant solubility. We suggest a qualitative explanation of the phenomenon, which reasonably agrees with our experimental observations.     

Photochemical reduction of transition metal substituted heteropoly anions in nonpolar solutions

Photochromism of [SiW11O39Ni(X)]6- as a tetraheptylammonium salt in various solvents under broadband UV light is observed in the presence of alcohols. The reaction proceeds faster with benzyl alcohol than with ethanol. Benzaldehyde is identified as the oxidized product of benzyl alcohol. Photochemistry is a reliable means to produce stable reduced transition metal substituted heteropoly tungstates in nonpolar media, where they hold promise as multielectron reduction catalysts. Preliminary reactivity toward CO2 reduction is demonstrated.     

The spectrochemical properties of noncubic transition metal complexes in solutions. Part I. Mixed tetragonal distorted nickel(II) pyridine complexes in chloroform

Summary The electronic spectra of tetragonal nickel(II) complexestrans-[Ni(Py)₄L₂], (Py=pyridine and L=NCS, Cl, Br, or I) have been measured in a 10% pyridine solution in chloroform at room temperature. The experimental curves were resolved by Gaussian analysis. The various ligand field parameters are discussed in terms of their chemical utility and their relation to ligand-field strengths. The ligand field parameters were examined by the dumped nonlinear least-squares algorithm (Gauss-Newton method) and Powell solution-seeking (nongradient) algorithm. The standard deviations of the parameters have been obtained from the former. Finally, it was found that the structure of the complexes in chloroform solution are much the same as in the solid state.     

Positronium formation at low temperatures: the role of trapped electrons

Measurements have been carried out of electron spin densities (by electron spin resonance technique) and positronium (Ps) formation probability as functions of Co-60 γ-irradiation dose in poly(methyl methacrylate) and linear poly(ethylene) at 77 K. We observe a linear relationship between the enhancement of the Ps formation and the density of trapped electrons in both polymers. This clear correlation strongly supports the previous suggestion by the authors that the increase in Ps formation with time (that has been observed at low temperatures for a number of polymers) can be explained as a reaction of free positrons with trapped electrons produced by the previously injected positrons.     

Reactions involving transition metals : XIX. Some reactions of perfluoronorbornadiene with low valent transition metal complexes

Perfluoronorbornadiene reacts with the compounds [M(PPh₃)₄] (M = Pt, Pd) and [IrCl(CO)(PMePh₂)₂] to give the adducts [(C₇F₈)M(PPh₃)₂] and [(C₇F₈)IrCl(CO)(PMePh₂)₂] in which one of the double bonds is coordinated to the metal atom. The platinum complex reacts further with [Pt(PPh₃)₄] to give [(C₇F₈){Pt(PPh₃)₂}₂] having both double bonds coordinated to a Pt atom. The carbonylmetal anions [M^?] react to form the mono-substitution products [(C₇F₇)M] (M = Mn(CO)₅, Re(CO)₅, Ir(CO)₂(PPh₃)₂, Rh(CO)₂(PPh₃)₂), but the use of an excess of [Fe(CO)₂(η-C₅H₆)]^? leads to substitution of one fluorine atom on each of the double bonds. The complex having M = Mn(CO)₅ reacts with [Pt(PPh₃)₄] to afford the derivative [(C₇F₇){Mn(CO)₄(PPh₃)}{Pt(PPh₃)₂}], and the compound where M = Ir(CO)₂(PPh₃)₂ undergoes an oxidative addition reaction with acetyl chloride. Oxidative coupling products have been isolated on UV irradiation of a mixture of perfluoronorbornadiene and [Fe(η⁴-CH₂CRCHCH₂)(CO)₃] (R = H, Me), and under similar conditions the reaction with Fe(CO)₅ affords [(C₇F₈)Fe(CO)₄] in very low yield.     

Semi-empirical LCAO-Xα theory for transition metal complexes. I. An outline of the theory

A semi-empirical theory for transition metal complexes is presented. Unusual aspects of the theory are (1) employment of Xα theory, (2) adoption of theoretical exchange parameter, (3) exclusion of (n + 1)s and (n + 1)p atomic orbitals of a nd-transition metal, and (4) variation of atomic orbitals in LCAO method. Also, an improved Mulliken approximation is proposed and used to simplify the LCAO-Xα equations.