Theoretical Analysis of Peroxynitrous Acid: Characterization of Its Elusive Biradicaloid (HO···ONO) Singlet States
- 1 December 2003
- journal article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 125 (52) , 16204-16205
- https://doi.org/10.1021/ja038524x
Abstract
Various high levels of theory (DFT, QCISD, BD(TQ), and CASSCF) have been applied to the characterization of two higher-lying biradicaloid singlet states of peroxynitrous acid. A singlet minimum (cis-2) was located that had an elongated O−O distance of 2.17 Å and was only 14.4 kcal/mol [UB3LYP/6-311+G(3df,2p)] higher in energy than its cis-peroxynitrous acid ground-state precursor. A trans metastable higher-lying singlet (trans-2) was 12.8 kcal/mol higher in energy than ground-state HO−ONO. Complete active space calculations [CAS(12,10)/6-311+G(d,p)] predicted the optimized geometries of these cis and trans metastable singlets to be quite close to those obtained with the DFT method. Geometry optimization of both cis- and trans-2 within the COSMO solvent model suggest that both exist as energy minima in polar media with elongated O−O distances of 2.14 and 2.09 Å. Both cis- and trans-2 exist as hydrogen-bonded complexes with several water molecules. These collective data suggest that solvated forms of cis-2·3H2O and trans-2·3H2O represent the elusive higher-lying biradicaloid minima that have been previously advocated (J. Am. Chem. Soc.1996, 118, 3125) as the metastable forms of peroxynitrous acid (HOONO*).Keywords
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