{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T19:48:11Z","timestamp":1760298491349,"version":"3.41.2"},"reference-count":87,"publisher":"AIP Publishing","issue":"11","content-domain":{"domain":["pubs.aip.org"],"crossmark-restriction":true},"short-container-title":[],"published-print":{"date-parts":[[2012,3,21]]},"abstract":"<jats:p>We report an ab initio multireference perturbation theory investigation of the HO2 + H2O + O3 reaction, with particular emphasis on the barrier heights for two possible reaction mechanisms: oxygen abstraction and hydrogen abstraction, which are identified by two distinct saddle points. These saddle points and the corresponding pre-reactive complexes were optimized at the CASSCF(11,11) level while the single point energies were calculated with three different MRPT2 theories: MRMP, CASPT2, and SC-NEVPT2. Special attention has been drawn on the \u201cintruder state\u201d problem and the effect of its corrections on the relative energies. The results were then compared with single reference coupled-cluster methods and also with our recently obtained Kohn-Sham density functional theory (KS-DFT) calculations [L. P. Viegas and A. J. C. Varandas, Chem. Phys.,10.1016\/j.chemphys.2011.04.022 (2011)]. It is found that the relative energies of the pre-reactive complexes have a very good agreement while the MRPT2 classical barrier heights are considerably higher than the KS-DFT ones, with the SC-NEVPT2 calculations having the highest energies between the MRPT2 methods. Possible explanations have been given to account for these differences.<\/jats:p>","DOI":"10.1063\/1.3695371","type":"journal-article","created":{"date-parts":[[2012,3,22]],"date-time":"2012-03-22T15:58:50Z","timestamp":1332431930000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":10,"title":["A detailed test study of barrier heights for the HO2 + H2O + O3 reaction with various forms of multireference perturbation theory"],"prefix":"10.1063","volume":"136","author":[{"given":"Lu\u00eds P.","family":"Viegas","sequence":"first","affiliation":[{"name":"Universidade de Coimbra Departamento de Qu\u00edmica, , 3004-535 Coimbra, Portugal"}]},{"given":"Ant\u00f3nio J. 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