Ab initio studies of structural features not easily amenable to experiment. 3. The influence of lone pair orbital interactions on molecular structure

by Williams, James Odell; Scarsdale, J. N.; Schäfer, Lothar

The characteristic structural asymmetries and distortions of A-X-Y-B systems in which an electron lone pair is at Y are discussed on the basis of the completely relaxed ab initio equilibrium geometries of a number of representative systems including various conformations of methanediol, hydrazine, 1,2-dimethylhydrazine and of compounds with CH3groups adjacent to -OH, -OCH3, -NH, -NCH3and C(pi). It is found that, regardless of quantitative overlap and energy gap factors, all calculated trends in the relative extensions of bond distances and bond angles can be correlated in every detail to qualitative predictions based only on the orientational aspects of orbital interaction concepts.

Journal
Journal of Molecular Structure-Theochem
Volume
76
Issue
1
Year
1981
Start Page
11
ISBN/ISSN
2210-2728; 0166-1280
DOI
10.1016/0166-1280(81)85109-3