MP2/6-311++G(2d,2p) level optimized geometry for LiF–LiF–XF (X = F, Cl, Br).
The molecular electrostatic potential of (a) LiF–F2 (the lithium atom is to the far left; the three fluorine atoms are somewhat collinear) and (b) LiF-LiF–F2 (the two lithium atoms are at the extremes in the centre of the plot; the three fluorine atoms to the right are collinear; the fourth is to the far left) generated by mapping the MP2/6-311++G(2d,2p) electrostatic potential onto the molecular electron density surface (0.001 electron/bohr3) (kcal mol−1). Colour ranges: Red – greater than 100, yellow – between 100 and 50, green – between 50 and 0, blue – less than 0 (negative).
Interaction energy, selected bond lengths (r), and angles for LiF⋯F2 and LiF⋯LiF⋯F2 complexes. The counterpoise-corrected interaction energy (ΔE CP) is included. The results for LiF⋯F2 are in brackets. Refer to Fig. 1 for the structure of the trimer. The LiF⋯F2 dimer structure is the trimer structure with the LicFc molecule absent.
Selected MP2/6-311++G(2d,2p) properties for LiaFa⋯XbFb (in brackets), LicFc⋯LiaFa⋯XbFb, and HFc⋯LiaFa⋯XbFb (X = F, Cl, Br) clusters. The energies are in kJ/mol, bond lengths in Å, angles in degrees, and the harmonic vibrational frequency shift (Δω) in cm−1. The labeling of the atoms is the same as that used in Fig. 1 , with H replacing Lic for the HF-containing trimers.
MP2/6-311++G(2d,2p) pairwise additive and non-additive contributions to ΔE: E non-add = ΔE − (ΔE ab + ΔE bc + ΔE ac) and ΔE ab, ΔE bc, and ΔE ac are calculated at the geometry of each pair in the optimized trimer. The labeling of the atoms is the same as that used in Fig. 1 , with H replacing Lic for the HF-containing trimers.
QTAIM electron density (ρ) and the negative of the Laplacian of the electron density (L) at the bond critical points (bcp) in LiF⋯LiF⋯F2 and HF⋯LiF⋯F2 computed at the MP2/6-311++G(2d,2p) level of theory. Refer to Fig. 1 for the labeling of the atoms.
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