An ab initio study of nitrous acid: geometries, force constants, fundamental frequencies, and potential surface for cis-trans isomerization.

by Coffin, J. M.; Pulay, Peter

The geometries, quadratic force fields, and fundamental vibrational frequencies of cis- and trans-nitrous acid were determined by using local 4th-order Moller-Plesset perturbation theory, and also 2-pair generalized valence bond wave functions. The Hartree-Fock approximation is inadequate for this mol., due to strong electron correlation. The theor. force field for the trans isomer agrees, after scaling, very well with the exptl. values of Deeley and Mills. The exptl. force field of the cis isomer is less accurately known and the present results are probably the most reliable date available. The energies and force constants along the cis-trans isomerization path were determined for future studies of the dynamics of the isomerization reaction.

Journal
Journal of Physical Chemistry
Volume
95
Issue
1
Year
1991
Start Page
118-122
URL
https://dx.doi.org/10.1021/j100154a027
ISBN/ISSN
0022-3654
DOI
10.1021/j100154a027