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The transition from the open minimum to the ring minimum on the ground state and on the lowest excited state of like symmetry in ozone: A configuration interaction study

TitleThe transition from the open minimum to the ring minimum on the ground state and on the lowest excited state of like symmetry in ozone: A configuration interaction study
Publication TypeJournal Article
Year of Publication2016
AuthorsTheis, D, Ivanic, J, Windus, TL, Ruedenberg, K
JournalJournal of Chemical Physics
Volume144
Pagination104304
Date Published03
Type of ArticleArticle
ISBN Number0021-9606
Accession NumberWOS:000372974600018
Keywordsatmospheric ozone, chemistry, conical intersection, consistent-field method, correlation-energy extrapolation, dissociation threshold, lying electronic states, molecular-dynamics, multiple active spaces, physics, theoretical evidence, variable occupations
Abstract

olation method was shown to be very accurate. On the other hand, none of the CI expansions were found to have converged to millihartree (mh) accuracy at the quadruple excitation level. The data suggest that convergence to mh accuracy is probably attained at the sextuple excitation level. On the 1(1)A(1) state, the present calculations yield the estimates of (ring minimum-open minimum) similar to 45-50 mh and (transition state-open minimum) similar to 85-90 mh. For the (2(1)A(1)-(1)A(1)) excitation energy, the estimate of similar to 130-170 mh is found at the open minimum and 270-310 mh at the ring minimum. At the transition state, the difference (2(1)A(1)-(1)A(1)) is found to be between 1 and 10 mh. The geometry of the transition state on the 1(1)A(1) surface and that of the minimum on the 2(1)A(1) surface nearly coincide. More accurate predictions of the energy differences also require CI expansions to at least sextuple excitations with respect to the valence space. For every wave function considered, the omission of the correlations of the 2s oxygen orbitals, which is a widely used approximation, was found to cause errors of about +/-10 mh with respect to the energy differences. (C) 2016 AIP Publishing LLC.

DOI10.1063/1.4942019
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Chemical Physics

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Alternate JournalJ. Chem. Phys.