ISSN:
0020-7608
Keywords:
Computational Chemistry and Molecular Modeling
;
Atomic, Molecular and Optical Physics
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The barriers to internal rotation about the N—C bond of formamide and the formamide-H2O complex have been examined by ab initio quantum chemistry methods. Both self-consistent field and correlated approaches have been utilized to determine the geometries, energies, and local harmonic vibrational frequencies of the minimum-energy and transition-state structures of these two systems. We find that formamide's rotation barrier of 14-15 kcal/mol is increased to 16-18 kcal/mol when a single H2O molecule is attached. This result contrasts with the effect of a single H2O solvent molecule on the barrier to tautomerization of formamide (to form formamidic acid HN—CHOH) for which a barrier lowering of ca. 20 kcal/mol has been observed. The rotation barriers obtained for formamide and for its H2O complex are compared with barriers obtained experimentally in various solvents. © 1993 John Wiley & Sons, Inc.
Additional Material:
4 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/qua.560450202
