ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
Ab initio molecular electronic structure methods have been used, in conjunction with large basis sets, to investigate the possible existence of isomers of the conventional C2v open-chain NO2 and its anion, NO−2. Equilibrium geometries have been optimized and harmonic vibrational frequencies obtained for both the "peroxy'' and cyclic isomers of these species at the self-consistent-field (SCF), single and double excitation configuration interaction (CISD), coupled cluster including all single and double substitutions (CCSD), and complete active space (CAS) SCF levels of theory utilizing both double-zeta plus polarization (DZ+P) and quadruple-zeta plus double polarization (QZ+2P) basis sets. For comparison, "normal'' (C2v open-chain) NO−2 was also studied. Diffuse functions were added to these basis sets to provide a better description of the electron densities of the anionic isomers. The four peroxy and cyclic structures investigated were predicted to be relatively high-lying (≥60 kcal mol−1) minima at most levels of theory considered. Moreover, interconversion between the C2v and Cs open-chain forms appears unlikely both for NO2 and NO−2.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.459989
Permalink