Instantaneous collision complexes in molten alkali halides: Picosecond dynamics from low-frequency Raman data

Abstract

The picosecond dynamics of molten alkali halides is discussed, and the low-frequency Raman spectra of molten LiCl, CsCl, and the LiCl–CsCl eutectic are fitted to the model enabling to obtain the times of vibrational dephasing, τV and vibrational frequency modulation τω. In terms of the Wilmshurst criterion [J. Chem. Phys. 39, 1779 (1963)] and using the data of NMR studies and molecular dynamics simulations, a conclusion is drawn that molten alkali halides cannot contain long-lived stable complexes with lifetimes greater than 10−8 s. The low-frequency Raman spectra of molten alkali halides and their mixtures probe the presence of instantaneous spatial configurations of MXn−n+1 type, where M+ is the alkali metal cation and X− is the halide anion existing in melts during the time intervals equal to the time of duration of collision of oppositely charged ions τd, which is less than 0.5 ps. This time is sufficient to a collision complex to execute several (at least one) vibrations. Vibrational dephasing and modulation processes elapse during this same time, thereby indicating the instantaneous nature of configurations in question. To discern between short-lived and long-lived complexes, we propose relations between the minimal damping time of the probe oscillator set equal to the half-period of vibration T/2, τV, τω, and τd, as well as the time between collisions τBC. The duration of an act resulting in the vibrational phase shift (or energy transfer) must be equal to (or longer than) the half-period of vibration of the probe oscillator, τV⩾T/2. The modulation time may vary from this same half-period of vibration or the time between collisions τBC to very long times, τω⩾T/2, τω⩾τBC. For short-lived complexes, the longest of two characteristic times describing the phase decay cannot exceed possible duration of collision, τω⩽τd, τV⩽τd. Cs-containing configurations follow this definition and therefore should be considered instantaneous short-lived collision complexes: their τV≈T/2∼0.1 ps, and τω≈τBC∼0.03 ps. Li-containing configurations appear to be relatively long-lived: their lifetimes could be associated with τω∼0.17 ps, which is several times longer than any other shortest possible characteristic time in the system (τBC∼0.026 ps or T/2∼0.05 ps). In light of these conclusions, an a priori assumption of autocomplex MX4n−4 anions and Mn+ cations as being structural elements of molten halides made in the so-called autocomplex model by Smirnov, Shabanov, and Khaimenov [Elektrohim. 2, 1240 (1966)] is discussed, and the autocomplexes are identified as instantaneous short-lived configurations detectable by the Raman method.

Novel Approaches in Spectroscopy of Interparticle Inter-Actions. Vibrational Line Profiles and Anomalous Non-Coincidence Effects

“…In Refs [53,54], the picosecond dynamics of molten halides has been studied and relations have been found enabling one to discern between instantaneous, short-lived and long-lived species in liquids. These are based on the comparison of the minimal damping time ofthe probe oscillator set equal to the half-period of vibration T/2, Tv, T., and Td, as well as the time between collisions T8c:…”

An in situ spectroscopic study of the local structure of oxyfluoride melts: NMR insights into the speciation in molten LiF–LaF3–Li2O systems

“…[1][2][3] In molten fluorides, such information has been experimentally brought by Raman, 4-6 NMR 7-10 and EXAFS [11][12][13][14] spectroscopies. [1][2][3] In molten fluorides, such information has been experimentally brought by Raman, 4-6 NMR 7-10 and EXAFS [11][12][13][14] spectroscopies.…”

Spectroscopy of interparticle interactions in ionic and molecular liquids: Novel approaches

“…The data presented in ref. [17] and this paper may signify that the main idea of the autocomplex model is not far from reality: autocomplexes may be identified as instantaneous and/or short-lived collision complexes.…”

“…As far as overlap lines are concerned, it has been successfully employed in order to obtain vibrational relaxation parameters of isotopic species in liquid carbon tetrachloride from the isotopic structure of the ν 1 line in the isotropic Raman spectrum [16] (see Fig. 1), to characterize instantaneous collision complexes in molten alkali halides [17], and to search for indicators of short-time interactions related to cooperativity in glass-forming liquids [18]. In the next sections, we consider some of these results in more detail.…”

“…[17], the Raman spectra of molten alkali halides have been investigated using the method described in ref. [2].…”