1 Identification of anhydrous CaCl 2 and KCaCl 3 in natural inclusions by 1 Raman spectroscopy 2 GRISHINA Svetlana 1 , KODċRA Peter 2 , URIARTE Lucas M. 3 , DUBESSY Jean 3 , 3 ORESHONKOV Aleksandr 4,5, , GORYAINOV Sergey 1 , ŠIMKO František 6 , YAKOVLEV Igor 1 . 4 ROGINSKII Evgenii M. 7 5 1: Sobolev Institute of Geology and Mineralogy Siberian Branch of the Russian Academy of Sciences, Koptuyg 6 Avenue 3, Novosibirsk 630090, Russia 7 2: Department of Economic Geology, Comenius University, Faculty of Natural Sciences, Ilkoviþova 6, 842 15 8 Bratislava, Slovakia 9 3: Université de Lorraine, CNRS, CREGU, GeoRessources laboratory (UMR 7359), Vandoeuvre-lès-Nancy, BP- 10 70239, F-54506, France 11 4: Kirensky Institute of Physics, Federal Research Center KSC SB RAS Akademgorodok 50/38, Krasnoyarsk 12 660036, Russia 13 5: Siberian Federal University, Svobodniy 79, Krasnoyarsk 660079, Russia 14 6: Institute of Inorganic Chemistry, Slovak Academy of Sciences, Dúbravská cesta 9, 845 36 Bratislava, Slovakia 15 7: Ioffe Institute, St. Petersburg 194021, Russia 16 17 Keywords: polymorphs CaCl 2 , Raman spectra, magma-salt interaction, chlorocalcite, daughter 18 mineral, ab initio calculations 19 Author for checking the proof: KodČra Peter 20 e-mail peter.kodera@gmail.com 21 22 ABSTRACT 23 Anhydrous chlorides - CaCl 2 , and KCaCl 3 (chlorocalcite) were identified as mineral 24 inclusions in halite from the Siberian Large Igneous Province at the contact of magmatic 25 intrusions and evaporates. Chlorocalcite was also found as daughter mineral in polyphase 26 hypersaline inclusions. While Raman spectra of KCaCl 3 (chlorocalcite) in natural inclusions are 27 similar to spectra of synthetic analogue, the Raman spectra of natural CaCl 2 do not correspond to 28 the published Raman spectra of synthetic CaCl 2 . Simulations of Raman spectra using ab initio 29 density-functional theory (DFT) allowed us to calculate the spectra of individual polymorphs of 30 CaCl 2 and to discriminate anhydrous CaCl 2 phases in natural inclusions and synthetic CaCl 2 . In 31