Quantum-Chemical Study of the Charge Transfer Mechanism in the MgTiF6–12MgCl2 System

Study of the Electron Transfer in Titanium Containing Melts by Electrochemical and Quantum-Chemical Methods

“…In our experience, such a model can be successfully used to study electron transfer and is qualitatively consistent with the experiment. 29,30,32,33 The probability of electron transfer from the electrode surface to the model system under study is determined primarily by the nature of the lowest unoccupied molecular orbital (LUMO) and neighboring unoccupied molecular orbitals (UMOs). The obtained experimental data on the standard rate constants of charge transfer and our previous electrochemical investigations indicate the bridge mechanism of charge transfer.…”

“…For electrolytes based on alkaline earth metal halides, this can be, for example, MTiF 6 + 12MX 2 type systems (M-Mg, Ca, Sr, Ba; X-F, Cl). 21,29,30 The search for a transition state by standard methods will require enormous computer time and is almost unrealistic. In this paper, we proposed another approach, which is based on the analysis of frontier molecular orbitals (FMO) under various deformations of the initial structure.…”

“…Earlier, some possibilities of the FMO method were illustrated based on the analysis of the model system MgTiF 6 + 12MgCl 2 . 29 In this work, the possibility of mixing closely lying boundary molecular orbitals (MOs) was taken into account. When considering electron transfer in the MgTiF 6 + 12MgCl 2 system, it was found that for this system the structures most promising for charge transfer turned out to be structures in which the Ti-F bond lengths were compressed as a result of the completely symmetric vibration of the titanium complex.…”

“…In addition to this parameter, the shift of the boundary calcium and chlorine ions from the reference state also varied in this paper. 29 Then it was checked whether the type of the highest occupied molecular orbital (HOMO) of the system after electron transfer allows the localization of an additional electron on the complex in the process of complex relaxation during its diffusion into the depth of the system. 29 In this regard, the use of the FMO method for searching for the transition state in other model systems is highly interest.…”

“…29 Then it was checked whether the type of the highest occupied molecular orbital (HOMO) of the system after electron transfer allows the localization of an additional electron on the complex in the process of complex relaxation during its diffusion into the depth of the system. 29 In this regard, the use of the FMO method for searching for the transition state in other model systems is highly interest. The aim of this work was investigation of electron transfer process in titanium containing melts with addition of the CaCl 2 by cyclic voltammetry and quantum-chemical analysis of frontier molecular orbitals.…”