1991/03/01 by Luis Seijo, Zoila Barandiarán, Sigeru Huzinaga · 3 citations
Chemistry · Materials Science · #Ab initio #Alkali metal #Alkaline earth metal #Atomic orbital #Atomic physics #Barium #Basis set #Bent molecular geometry #Bond length #Boron and Carbon Nanomaterials Research #Chemistry #Computational chemistry #Density functional theory #Geometry #Ground state #Inorganic Chemistry and Materials #Inorganic chemistry #MXene and MAX Phase Materials #Molecular geometry #Molecule #Physics #Quantum mechanics #Valence (chemistry)
paper · doi:10.1063/1.459748
openalex publication_date 1991/03/01 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/23
The ground state equilibrium geometry of alkaline earth dihalides MX2 (M=Mg, Ca, Sr, Ba; X=F, Cl, Br, I) has been optimized at the Hartree–Fock (HF) level using the Cowan–Griffin relativistic ab initio model potential method and a uniformly good, extended, spd valence basis set. The results show that, according to the method, all magnesium dihalides and CaCl2, CaBr2, and CaI2 are linear, SrF2 and all barium dihalides are bent, and CaF2 and SrCl2, SrBr2, and SrI2 are quasilinear molecules. The alkaline earth (n−1)d orbitals are shown to be responsible for the bending of the heavier molecules while their (n−1)p orbitals contribute considerably to the final quantitative prediction of the apex angle and the relative stability of the bent structures. Relativistic effects are shown to be very small on the bond distances and vibrational frequencies; they are important on the size of the bending barrier of the bent molecules. The results obtained are compared to previous theoretical studies and provide some insight in the interpretation of the contradictory experimental conclusions.