The HgS and HgSe films were obtained by chemical deposition technique from an aqueous solution of mercury(II) salt, complexing and chalcogenizing agents. For the obtaining of Hg(II) complexes during the HgS films synthesis thiourea was used, and during the HgSe films synthesis – potassium iodide, potassium rhodanide and sodium thiosulfate. By the X-ray phase analysis was confirmed the formation of desired compounds, as well as the formation of Hg3I2Se2 ternary compound in the case of potassium iodide use during the synthesis of HgSe films. The main factors that affect on the metal sulfides films formation during their chemical synthesis from aqueous solution were described. On the basis of literature data analysis are proposed the hypothesis about the formation of intermediates, reactive complexes, associates, clusters, structures with colloidal nature which are structural links in the process of mercury chalcogenides film synthesis due to co-operative and fluctuation phenomenas in the working solution. The quantum-chemical modeling of synthesis chemistry of HgS films with the use of thiourea and HgSe films with the use of potassium iodide, potassium rhodanide and sodium thiosulfate was carried out on the basis of the proposed hypothesis. The comparison of HgS and HgSe synthesis processes with proposed complexing agents based on the calculated energy diagrams of the modeled stages of synthesis process by PM6 and PM7 semi-empirical methods in MOPAC2012 program package has been made. It was found that the HgS films synthesis with thiourea should be carried out at elevated temperatures, as a result of the smaller system energy change (ΔE = 119 kJ/mol) compared to ΔЕ for the HgSe films synthesis (ΔЕ = 450-550 kJ/mol). A larger value of a system energy change for Hg3I2Se2 synthesis (ΔE = 550 kJ/mol) as compared to HgSe films deposition (ΔЕ = 438 kJ/mol) with the potassium iodide use as a complexing agent, indicates the possibility of both products forming, which has been confirmed experimentally. A similar nature of the system energy changes and the proximity of ΔЕ values of the modeling stages of HgSe films synthesis with the use of different complexing agents (∆Е = 430-550 kJ/mol) pointing out the similarity of their synthesis chemistry.
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