Ab initio molecular orbital calculations on ion-molecule and ion pair-molecule complexes of the water-lithium cyanide system

Ab initio molecular orbital (MO) calculations with the 3-21G and 6-31G basis sets were performed on a series of ion-molecule and ion pair-molecule complexes for the H2O + LiCN system. Stabilisation energies (with counter-poise corrections), geometrical parameters, internal force constants and harmonic vibrational frequencies were evaluated for 16 structures of interest. Although the interaction energies are smaller, the geometries and relative stabilities of the monohydrated contact ion pair are reminiscent of those computed for the complexes of the individual ions. Thus, interaction of the oxygen lone pair with lithium leads to a highly stabilised C2v structure, while the coordination of water to the cyanide ion involves a slightly non-linear hydrogen bond. Symmetrical bifurcated structures are computed to be saddle points on the potential energy surface, and to have an imaginary frequency for the rocking mode of the water molecule. On optimisation the geometries of the solvent shared ion pair structures (e.g. Li+cdots, three dots, centered OH2cdots, three dots, centered CN−) revealed a proton transfer from the water molecule leading to hydrogen bonded forms such as Li-O-Hcdots, three dots, centered HCN. The variation in the force constants and harmonic frequencies in the various structures considered are discussed in terms of ion-molecular and ion pair-molecule interactions.

Elliptic flow of thermal photons in heavy-ion collisions at Relativistic Heavy Ion Collider and Large Hadron Collider

We calculate the thermal photon transverse momentum spectra and elliptic flow in $\sqrt{s_{NN}} = 200$ GeV Au+Au collisions at RHIC and in $\sqrt{s_{NN}} = 2.76$ TeV Pb+Pb collisions at the LHC, using an ideal-hydrodynamical framework which is constrained by the measured hadron spectra at RHIC and LHC. The sensitivity of the results to the QCD-matter equation of state and to the photon emission rates is studied, and the photon $v_2$ is discussed in the light of the photonic $p_T$ spectrum measured by the PHENIX Collaboration. In particular, we make a prediction for the thermal photon $p_T$ spectra and elliptic flow for the current LHC Pb+Pb collisions.

ChemInform Abstract: Synthesis of Anion-Deficient Layered Perovskites, ACa2Nb3-xMxO10-x (A: Rb, Cs; M: Al, Fe), Exhibiting Ion-Exchange and Intercalation. Evidence for the Formation of Layered Brownmillerites, ACa2Nb2AlO9 (A: Cs, H)

Anion-deficient layered perovskite oxides of the formula, ACa2Nb3-xMxO10-x (A = Rb, Cs; M = Al, Fe) for 0 < x less-than-or-equal-to 1.0, possessing tetragonal structures similar to the parent ACa2Nb3O10, have been synthesized. The interlayer A cations in these materials are readily exchanged with protons in aqueous HNO3 to give the protonated derivatives, HCa2Nb3-xMxO10-x; the latter are solid Bronsted acids intercalating a number of organic amines including aniline (pK(a) = 4.63). The distribution of acid sites in the interlayer region of HCa2Nb2MO9 inferred from n-alkylamine intercalation suggests that oxygen vacancies and Nb/M atoms are disordered in the ACa2Nb2MO9 samples prepared at 1100-1200-degrees-C. Annealing a disordered sample of CsCa2Nb2AlO9 for a long time at lower temperatures tends to order the Nb/Al atoms and oxygen vacancies to produce octahedral (NbO6/2)-tetrahedral (AlO4/2)-octahedral (NbO6/2) layer sequence reminiscent of the brownmillerite structure.

Non-linear optical response of rutile-related oxides, LiM(V)M(VI)O(6), and their derivatives obtained by ion-exchange and intercalation

Polycrystalline samples of oxides of the general formula LiM(V)M(VI)O(6) (M(V) = Nb, Ta; M(VI) = Mo, W), crystallizing in a non-centrosymmetric (space group P (4) over bar 2(1)m) trirutile structure, exhibit second harmonic generation (SHG) of 1064 nm radiation with efficiencies 15-45 times that of alpha-quartz; interestingly, the SHG response is retained by the protonated derivatives HM(V)M(VI)O(6) . xH(2)O, and their n-alkylamine intercalates as well.

Polar and nonpolar solvation dynamics, ion diffusion, and vibrational relaxation: Role of biphasic solvent response in chemical dynamics

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Seeded-growth, nanocrystal-fusion, ion-exchange and inorganic-ligand mediated formation of semiconductor-based colloidal heterostructured nanocrystals

This article highlights different synthetic strategies for the preparation of colloidal heterostructured nanocrystals, where at least one component of the constituent nanostructure is a semiconductor. Growth of shell material on a core nanocrystal acting as a seed for heterogeneous nucleation of the shell has been discussed. This seeded-growth technique, being one of the most heavily explored mechanisms, has already been discussed in many other excellent review articles. However, here our discussion has been focused differently based on composition (semiconductor@semiconductor, magnet@semiconductor, metal@semiconductor and vice versa), shape anisotropy of the shell growth, and synthetic methodology such as one-step vs. multi-step. The relatively less explored strategy of preparing heterostructures via colloidal sintering of different nanostructures, known as nanocrystal-fusion, has been reviewed here. The ion-exchange strategy, which has recently attracted huge research interest, where compositional tuning of nanocrystals can be achieved by exchanging either the cation or anion of a nanocrystal, has also been discussed. Specifically, controlled partial ion exchange has been critically reviewed as a viable synthetic strategy for the fabrication of heterostructures. Notably, we have also included the very recent methodology of utilizing inorganic ligands for the fabrication of heterostructured colloidal nanocrystals. This unique strategy of inorganic ligands has appeared as a new frontier for the synthesis of heterostructures and is reviewed in detail here for the first time. In all these cases, recent developments have been discussed with greater detail to add upon the existing reviews on this broad topic of semiconductor-based colloidal heterostructured nanocrystals.

Influence of ion energy and substrate temperature on the optical and electronic properties of tetrahedral amorphous carbon (ta-C) films

The properties of amorphous carbon (a-C) deposited using a filtered cathodic vacuum arc as a function of the ion energy and substrate temperature are reported. The sp3 fraction was found to strongly depend on the ion energy, giving a highly sp3 bonded a-C denoted as tetrahedral amorphous carbon (ta-C) at ion energies around 100 eV. The optical band gap was found to follow similar trends to other diamondlike carbon films, varying almost linearly with sp2 fraction. The dependence of the electronic properties are discussed in terms of models of the electronic structure of a-C. The structure of ta-C was also strongly dependent on the deposition temperature, changing sharply to sp2 above a transition temperature, T1, of ≈200°C. Furthermore, T1 was found to decrease with increasing ion energy. Most film properties, such as compressive stress and plasmon energy, were correlated to the sp3 fraction. However, the optical and electrical properties were found to undergo a more gradual transition with the deposition temperature which we attribute to the medium range order of sp2 sites. We attribute the variation in film properties with the deposition temperature to diffusion of interstitials to the surface above T1 due to thermal activation, leading to the relaxation of density in context of a growth model. © 1997 American Institute of Physics.

Studies of ion energy and yield from argon clusters heated by intense femtosecond laser pulses

Using time-of-flight spectrometry, the interaction of intense femtosecond laser pulses with argon clusters has been studied by measuring the energy and yield of emitted ions. With two different supersonic nozzles, the dependence of average ion energy (E) over bar on cluster size (n) over bar in a large range of (n) over bar approximate to 3 x 10(3) similar to 3 x 10(6) has been measured. The experimental results indicate that when the cluster size (n) over bar <= 3 x 10(5), the average ion energy (E) over bar proportional to (n) over bar (0.5), Coulomb explosion is the dominant expansion mechanism. Beyond this size, the average ion energy gets saturated gradually, the clusters exhibit a mixed Coulomb-hydrodynamic expansion behavior. We also find that with the increasing gas backing pressure, there is a maximum ion yield, the ion yield decreases as the gas backing pressure is further increased.

Part I. Influence of membrane morphology on ion-exchange and charge propagation in composite polyelectrolyte electrode coatings. Part II. Dynamic surface tension measurements of polarization relaxation at mercury pool electrodes by the method of Wilhelmy.

Part I. Novel composite polyelectrolyte materials were developed that exhibit desirable charge propagation and ion-retention properties. The morphology of electrode coatings cast from these materials was shown to be more important for its electrochemical behavior than its chemical composition.

Part II. The Wilhelmy plate technique for measuring dynamic surface tension was extended to electrified liquid-liquid interphases. The dynamical response of the aqueous NaF-mercury electrified interphase was examined by concomitant measurement of surface tension, current, and applied electrostatic potential. Observations of the surface tension response to linear sweep voltammetry and to step function perturbations in the applied electrostatic potential (e.g., chronotensiometry) provided strong evidence that relaxation processes proceed for time-periods that are at least an order of magnitude longer than the time periods necessary to establish diffusion equilibrium. The dynamical response of the surface tension is analyzed within the context of non-equilibrium thermodynamics and a kinetic model that requires three simultaneous first order processes.