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Ab Initio Calculations of Structure and Energetics of the Hypermetalated Hydrogen Oxide Molecules: Li 2 NaOH and LiNa 2 OH
Author(s) -
Shie YiShiau,
Ho JiaJen
Publication year - 1994
Publication title -
journal of the chinese chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.329
H-Index - 45
eISSN - 2192-6549
pISSN - 0009-4536
DOI - 10.1002/jccs.199400066
Subject(s) - chemistry , endothermic process , ab initio , dissociation (chemistry) , energetics , bond dissociation energy , density functional theory , ab initio quantum chemistry methods , molecule , hydrogen , crystallography , computational chemistry , thermodynamics , adsorption , organic chemistry , physics
We made ab initio electronic calculations of the structure and energetics of mixed hypermetalated hydrogen oxides, Li 2 NaOH and LiNa 2 OH. There exist five equilibrium geometries for each complex. In all levels of calculation the global minimum structure for Li 2 NaOH has C 2v symmetry and a large distance between sodium and oxygen, 4.24 Å (MP2/6‐31G*). The dissociation energies to all possible products were also calculated. Li 2 NaOH → Na + Li 2 OH δH = +25.33 kcal/mol (at MP4/6‐311++G**//6‐31G* + ZPE scaled by 0.9). All other dissociation processes are highly endothermic. Similar procedures were applied to LiNa 2 OH. The global minimum structure for LiNa 2 OH belongs to point group C s . It is also endothermic to all possible dissociation paths. LiNa 2 OH →Na + LiNaOH δH = +12.72 kcal/mol (at MP4/6‐311++G*//6‐31G* + ZPE scaled by 0.9). The nuclear repulsion energy is crucial in energetics of the structures. The distribution of electron density and bonding properties for these equilibrium structures were analyzed.