Experimental structural data for liquid Bi were used for estimation of the main structure parameters as well as the thermal expansion coefficient both in super cooled and superheated temperature ranges. It was shown that the equilibrium melt had a positive thermal expansion coefficient within a temperature range upon melting and a negative one at higher temperatures. The former was related to structure changes upon melting, whereas the latter with topologic disordering upon further heating. It was found that the superheated melt had a negative thermal expansion coefficient. The results obtained from structural data were compared with the thermal expansion coefficient calculated from the data of density for liquid Bi.
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