Absorption spectra in alkali halide crystals

A phenomenological model is presented which predicts the absorption energy of the first fundamental band in alkali halide crystals as well as impurity absorptions such as the hydride ion. Its basis is the electron transfer model of Hilsch and Pohl, but is considerably more satisfying since it utilizes kinetic energy terms for the absorption energy, and there is good to excellent agreement with the virial theorem.     

A mass-spectrometric determination of the work function of alkali metal halide crystals

Thermochemical cycles including experimentally measured enthalpies of sublimation of alkali metal halides in the form of M₂X⁺ and MX₂^∮ ionic clusters and MX molecules were used to calculate work functions for NaCl, NaBr, NaI, KCl, KBr, KI, RbCl, and RbI.     

A view and a review of melting of alkali metal halide crystals

Theoretical models for the melting of solids are inadequate because relatively little is known about the structures of liquids formed and the factors that control this phase transformation. In the present analysis of fusion phenomenon, usually considered to be a physical change, it is pointed out that, for many solids (e.g., metals and some simple ionic salts) melting involves the redistribution of primary valence bonds. Accordingly, this review includes examination some more chemical aspects of the controls of melting. The available data show that enthalpy and density changes during liquefaction and solidification of the metallic elements and of the alkali halides are small. From quantitative consideration of these values, it is concluded that ordered packing arrangements of atoms, ions, or molecules, comparable with those of crystals, must be extensively retained into the melt. The energy and molar volume changes on melting are too small to allow significant departure, in the liquid, from the regular, efficient space-filling arrays that characterize crystalline solids. The set/liq model for melting (dynamic equilibria between alternative ordered structures) is proposed to account for the properties of the liquid. A detailed and critical comparison of melting with solid state decompositions considers the kinetics and the mechanisms of the changes that occur during the supply/removal of energy to/from the melt/crystal contact interface. Other relevant aspects of melting are discussed including the factors that determine the magnitudes of the melting points of individual solids.     

Ammonium ions in alkali metal halide crystals: tunnelling and spin relaxation

We have used low energy inelastic neutron scattering spectroscopy to examine the tunnelling spectroscopy of the ammonium ion in the (NH4)0.02Rb(x)K(0.98-x)I system. The concentration of different species were varied as x increased, this was followed systematically and the first consistent assignment scheme for these features is given. Differences were also found for the relaxation rate of the spin temperature inversions that could be generated in these species. At a critical concentration--about x = 0.04 mole fraction--the relaxation rates of the species changed dramatically.     

A view and a review of the melting of alkali metal halide crystals

Summary A representational model, proposed to account for the physical changes that accompany the melting of alkali halides, was described in Part 1 [1]. The liquid is portrayed as undergoing continual dynamic structural reorganization of its constituent ions between individual small domains, zones of various regular, crystal-type arrays. These alternative arrangements are stabilized by the enthalpy of melting, which, in liquids, relaxes the restriction for solids that only the single, most stable, crystal structure can be present. The dynamic character of the melt accounts for its fluid character and the loss of long-range order [1, 2]. This model is extended here to consider the phase diagrams of binary, common ion, alkali halide mixtures comprehensively reviewed in [3]. Factors determining whether each of these yields a eutectic, or a solid solution, on cooling are discussed and several trends in the 70-phase diagrams are identified. Eutectic formation, involving maintenance of the liquid state below the melting points of the pure components, is ascribed to the participation, in an extended dynamic equilibrium, of additional domains having the regular structures characteristic of double salts. The known crystalline double binary halides [3], Li/Cs or Rb/F, Cl, Br or I, melt at temperatures well below those of the simpler pure component salts. It is concluded that the set/liq model for melting, proposed in [1, 2], accounts for some important properties of the phase diagrams presented in [3].     

A view and a review of the melting of alkali metal halide crystals

Summary Although melting is a most familiar physical phenomenon, the nature of the structural changes that occur when crystals melt are not known in detail. The present article considers the structural implications of the changes in physical properties that occur at the melting points, T_m, of the alkali halides. This group of solids was selected for comparative examination because the simple crystal lattices are similar and reliable data are available for this physical change. For most of these salts, the theoretical lattice energies for alternative, regular ionic packing in 4:4, 6:6 and 8:8 coordination arrangements are comparable. Density differences between each solid and liquid at T_mare small. To explain the pattern of quantitative results, it is suggested that the melt is composed of numerous small domains, within each of which the ions form regular (crystal-type) structures (regliq). The liquid is portrayed as an assemblage of such domains representing more than a single coordination structure and between which dynamic equilibria maintain continual and rapid transfers of ions. T_mis identified as the temperature at which more than a single (regular) structure can coexist. The interdomain (imperfect and constantly rearranging) material (irregliq) cannot withstand shear, giving the melt its fluid, flow properties. From the physical evidence, it is demonstrated that the structural changes on melting are small: these can accommodate only minor modifications of the dispositions of all, or most, ions or larger changes for only a small fraction. This proposed representation, the set/liq melt model, may have wider applicability.     

Ab initio calculations for absorption and emission energies of alkali halide crystals doped with thallium

We calculate transition energies associated with optical properties of thallium doping in alkali halide crystals via an atomic cluster of minimal size where an sp‐valence‐shell impurity enters as a substitutional defect in the model crystal. Hartree–Fock (HF), density functional theory (DFT), and configuration interaction (CI) [CIS (CI with single excitation) and QCISD (single plus double and quadruple excitation)] calculations are performed to theoretically obtain the absorption and emission energies as vertical transitions evaluated at the ground and first excited‐state optimized geometries, respectively, where the optimization is carried out separately with the HF and DFT methods. © 2000 John Wiley & Sons, Inc. Int J Quant Chem 77: 785–790, 2000     

Sulfoxide-mediated Umpolung of alkali halide salts

A new protocol for the direct two-electron oxidative Umpolung of alkali halide salts is reported. This procedure, relying on the use of a commercially available sulfoxide as the oxidant, allows the electrophilic halogenation of carbonyl compounds as well as halolactonisation reactions to proceed from the corresponding sodium salts, at room temperature and under mild conditions.     

Infrared multiphoton excitation of small molecules

The collisionless infrared excitation by short CO₂ laser pulses of the molecules SO₂, OCS, NO₂, NH₃ and DN₃ is compared with that of larger molecules. The average number of photons absorbed per molecule and the fraction of molecules dissociated depends predominantly on the laser intensity, while for larger molecules with higher densities of vibrational states the excitation is primarily determined by the laser fluence.     

Potential functions for alkali halide molecules

Repulsion and dispersion parameters for alkali–metal halide diatomic molecules were computed by ionic Rittner and truncated Rittner models with radial dependent repulsion terms. Experimental data on the bond energies, the equilibrium interionic distances, and the spectroscopic frequencies were employed for the purpose. The polarizabilities used were also computed from the experimental dipole moments of alkali–metal halides. The potential parameters obtained were compared with parameters from other sources and checked for consistency. The computed potential parameters of alkali–metal halide monomer molecules were used to predict the energetics and geometries for alkali–metal halide dimer molecules. The predicted values are in good agreement with experiment and other calculations indicating the consistency and reliability of the potential employed. Although the magnitude of repulsive and dispersive energy terms varies with potential functions employed, the difference between the two for a molecule is constant. The repulsive term is more sensitive than the attractive term. The uncertainty in the exponential repulsion results in an inaccurate representation of the attractive contribution. Introduction of the radial-dependent repulsion term changes the relative magnitudes of repulsive and dispersive parameters and hence the relative contribution to the total potential with monomers. But this has no significant effect on the energetics and geometries of the dimers.     

Infrared multiphoton excitation of refractory metal clusters

Photoexcitation and photoionization experiments on small Tungsten and Niobium clusters were performed with a Q-switched Nd:YAG laser (1064 nm) and a reflectron type time-of-flight mass spectrometer. For low laser fluences the monomer and very small clusters do not show up in the mass spectra. Furthermore, the detected cluster ions show very asymmetric peak shapes caused by delayed ionization (thermionic emission). For high photon fluences photoions with up to charge state +3 could be detected.     

Improved interaction potential for alkali halide molecules

An improved interaction potential has been devised for diatomic alkali halide molecules. This potential, in addition to similar attraction terms as in the Rittner potential, includes a new exponential for the short-range repulsion. The constant m in the exponential is seen to be well expressible in terms of the parameters of the Rittner potential. The new potential is also correlated with different properties, as for example, effective charges, effective radii, effective principal quantum numbers, etc., of the combining ions. Various spectroscopic constants, viz., the ionic dissociation energy D_i, the vibrational–rotational coupling constant α_e, the vibrational anharmonicity constant ω_ex_e, as well as two second-order spectroscopic constants γ_e and β_e have been calculated for this and for the Rittner potential. From comparisons between these two potentials, the new one has been observed better than the other.     

Formation of selectivity in molecular isomerization by the IR multiphoton excitation

The formation mechanism of the selectivity of IR laser isomerization induced by vibrational multiphoton excitation is considered. The effective and highly selective isomerization of perfluorodimethyl ketene (CF₃)₂C=C=O into perfluoromethacrylic acid fluoride F₂C=C(CF₃)COF and perfluorocyclobutene into perfluorobutadiene upon pulse irradiation with a CO₂ laser and its second harmonic was performed. The conversion of (CF₃)₂C=C=O into F₂C=C(CF₃)COF was higher than 99%. A record-breaking conversion of 99.8% of the parent substance into the isomer was achieved in the case of perfluorocyclobutene isomerization into perfluorobutadiene. It was shown that the high selectivity of the laser-induced chemical reactions is mainly associated with the different levels of the vibrational excitation of the parent molecules and their isomers. The latter is due to the difference in the IR absorption spectra of different isomers, which allows for the excitation of the necessary component with a high selectivity.     

The molecular dynamics problem in multiphoton excitation

While the molecular dynamics for weakly coupled, harmonic oscillators undergoing infinitesimal amplitude displacements are well described by normal modes, and the other extreme — strongly coupled anharmonic, large amplitude oscillating units can be treated as though they are ergodic systems, so that only state densities are needed, intermediate cases are very difficult to analyze. Here we propose that some intermediate cases, wherein we seek relative rates for reaction induced by specific frequency excitation (three-center displacement reactions or dissociation), may be approximately estimated from a normal mode analysis by calculating increment in root mean square amplitudes for a suitable internal coordinate, upon specific multiple photon absorption. A test case is presented as an illustration.     

Ultrasound velocity in dissolving alkali halide melts

Ultrasound velocities in the molten exsolving mixtures (LiF + CsCl, LiF + KBr, LiF + RbBr, LiF + CsBr, LiF + KI, LiF + RbBr, and LiF + CsBr) were obtained along the saturation line over a wide temperature range using the acoustic method. The temperature dependences of properties far away from the critical temperature are close to linear and the temperature and composition factors are highly correlated. The difference between the magnitudes of sound velocity for the coexisting phases increases with the radii of ions in the mixtures. The linearity of the temperature dependence of the velocity, which is typical for all systems at relatively low temperatures, is violated when approaching the critical point of mixing, mainly due to sharp changes of the light phase state. Our results suggested a classical (mean-field) critical behavior of ionic melts.     

Vibronic and resonance Raman spectra of NO2impurity ions in the body-centered alkali halide crystals

The low-temperature resonance secondary radiation spectrum as well as the absorption and luminescence excitation spectra of NO₂⁻ impurity ions in cesium halides have been studied. The energy relaxation processes and NO₂⁻ equilibrium orientation and reorientation problems have also been discussed. It was shown that the systems under study were characterized by average Stokes' losses and strong lattice distortions, exemplified by the Generation of a number of low-frequency local and pseudolocal vibrations. The inhomogeneous broadening in CsCl-NO₂⁻ and CsI-NO₂⁻ spectra was extremely large for the simple molecular impurity systems, leading to the interesting peculiarities of energy relaxation processes. Unlike some alkali halide crystals with NaCl structure the impurity NO₂⁻ does not rotate in the lattices with CsCl structure. The NO₂⁻ equilibrium orientation in cesium halides was fixed: both the molecular axis and the axis perpendicular to the molecular plane were directed in (100) directions of the crystal.     

Formation of structured nanophases in halide crystals

When halide crystals KCl and NaCl are slightly doped by PbCl(2), (in orders of 10(-4)?mol/mol) the structurally stable nanophases ("quantum dots") are formed via nucleation within the bulks of their matrices. Using lattice modeling we have found in KCl-Pb system natural nucleation pathway from single impurity-vacancy complex to Suzuki phase, not demonstrated in previous analyses; further transition to PbCl(2) is difficult due to high stability of this phase. In the case of NaCl-Pb, no stable "end point" of aggregation was observed and our calculations suggest nucleation may readily proceed to large PbCl(2) clusters when initially formed platelike cluster reaches a certain critical thickness. These results coincide with our experimental data.     

Coupled dressed-states formalism for multiphoton excitation and population inversion by coherent pulses

We show how the single-mode Floquet theory, valid only for sinusoidal field problems, may be generalized to a coupled quasienergy (or dressed-) states formalism, allowing non-perturbative treatment of multiphoton excitation of multilevel quantum systems driven by non-sinusoidal coherent pulse fields. The method is illustrated by a case study of the adiabatic population inversion in a CO Morse oscillator.