Reduction in Hybridization: Lone Pairs Interacting with Empty p Orbitals

2020-01-17T16:55:53Z (GMT) by Edmund Doerkson Ryan Fortenberry

X−NH2 and X−OH (for X = Li, BeH, BH2, Na, MgH, and AlH2) exhibit a reduction in hybridization in the N and O atoms, and likely in F, as well. CCSD(T)-F12/cc-pVTZ-F12 optimizations for all combinations of atoms smaller than chlorine (excluding the noble gasses) where the standard valences are filled with hydrogen atoms give breaks in the expected periodic trends. While most bond energies for a given atom increase when bonded to all atoms across a given row in the period table, X−NH2, X−OH, and X−F actually have the strongest bonds with X = BH2 and AlH2. Furthermore, the buildup in bond energy from the alkali to alkaline-earth metals is steady, and the decrease to Group 14 and beyond is also steady. The interactions of X−NH2 and X−OH with X = Li, BeH, BH2, Na, MgH, and AlH2 also produce either linear or fully planar geometries. All of these factors imply that the lone pair on the N or O atoms are datively bonding with the empty p orbitals in the other atoms. This leads to a reduction in hybridization. The non-periodic strengths of these bonds have implications for the detection of molecules in space as well as in models for the formation of refractory molecules and condensation of mineral species in early stages of planet formation.