The Rigidity of the (BH4)-Anion Dispersed in Halides AX, A = Na, K; X = Cl, Br, I, and in MBH4 with M = Na, K, Rb, Cs

نویسندگان

چکیده

The B–H bond length of the borohydride anion (BH4?) in alkali metal borohydrides MBH4 with M = Na, K, Rb, Cs, and diluted different halide matrices, was investigated experimentally by infrared spectroscopy (FTIR) theoretically using first principles calculations. peak positions IR absorption spectra NaBH4 pressed at 754 MPa halides NaX KX X Cl, Br, I show significant variations indicating ion exchange effects between NaBH4. For NaBr, NaI, KBr KI pellets, indicate that BH4? could be highly AX matrix, which renders an isolation (i-BH4?). NaCl KCl a solution occurred only after further thermal treatment up to 450 °C. observed are discussed respect lattice parameter (a0), cation ratio (R rA/rX), standard enthalpy formation (?fH) ionic character (Ic) halides. A linear relation is obtained ?3(i-BH4?) short-range energies AX. Density functional theory (DFT) calculations generalized gradient approximation (GGA) level were used calculate vibrational frequencies ?4, ?3 ?2 + ?4 for series compositions Na(BH4)0.25X0.75 I, MBH4. theoretical experimental results same trends, rigidity failure Badger’s rule.

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ژورنال

عنوان ژورنال: Crystals

سال: 2022

ISSN: ['2073-4352']

DOI: https://doi.org/10.3390/cryst12040510