The electronic structure of metal-molten salt solutions: A tight-binding approach

Abstract

Universal tight binding model for chemical reactions in solution and at surfaces. I. Organic molecules J. Chem. Phys. 141, 044503 (2014); 10.1063/1.4887095 Tight-binding model and electronic structure of tetrahedral zirconium silicate J. Appl. Phys. 90, 4570 (2001); 10.1063/1.1406972 IR spectroscopy of aqueous alkali halide solutions: Pure salt-solvated water spectra and hydration numbers

Ultrafast dynamics of excess electrons in molten salts: Part II. Femtosecond investigations of Na–NaBr and Na–NaI melts

“…Alkali metal-alkali metal halide (M-MX) liquid solutions provide relatively simple examples of structurally disordered systems where the localization and dynamical behaviour of excess electrons can be studied at elevated temperatures. Several experimental [1][2][3][4][5][6][7] and theoretical [8][9][10][11][12][13] studies have been carried out to better understand the nature of electronic defects that are created when a metal is added to a metal salt solution. At elevated temperatures M-MX mixtures form solutions over a wide concentration range of added metal and exhibit a continuous transition from an ionic system to a typical electronic conducting liquid.…”

EMF‐Study of the thermodynamics of liquid Kx(KI)1‐x and Csx(CsI)1‐x melts

“…This microscopic picture is supported by theoretical studies, both ab initio MD calculations [6] and Monte carlo simulations with tight binding treatment of the electronic structure [7]. In this paper we present results from EMF-measurements of K,(KI),_*.…”

Time-resolved polaron dynamics in molten solutions of cesium-doped cesium iodide

“…It is obvious from Fig. 9 The asymmetric absorption spectrum of excess electrons in water ͑hydrated electron͒, on the other hand, is attributed to the transition of electrons from an s-like ground state to three bound, localized p-like excited states and to delocalized states at higher energy. As pointed out above, such a shift in the excitation region has no influence on the relaxation dynamics of excess electrons in these mixtures.…”

“…Understanding electron localization and mobility has been the focus of a number of experimental 1-6 and theoretical [7][8][9][10] investigations in disordered media such as solutions of alkali-metal-doped alkali halide mixtures ͑M -MX͒. Besides their chemical and electrochemical applications, these molten metal-salt solutions offer relatively simple prototype systems to study the influence of thermal and topological disorders over a wide concentration range of added metal.…”

“…2 As a result, excitation of excess electrons at a wavelength of 800 nm corresponds to a blue-part excitation in Cs-CsI, whereas in the case of Na-NaI and K-KCl melts, the excitation at the same wavelength is redshifted regarding the peak position of the stationary absorption spectrum. It is predicted that the density of states at the bottom of the conduction band in metal-molten salts into which the polarons are excited are of predominantly s character, 9,21 whereas in the case of hydrated electrons the excitation is shown to take place from an s-to a p-like state. Hence, the information obtained on the relaxation dynamics of excess electrons in this investigation together with the results in Na-NaX and K-KCl melts 5,6 will be very useful in improving the present knowledge on the nature of polarons in these melts and in testing the validity of simple models to explain, for example, electrical and optical properties of electronic defects in M -MX mixtures.…”