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A composite computational scheme developed in the present work contributes to solving this task for a challenging case of lanthanide-containing molecules. In the scheme, the highest-spin states whose wavefunctions are dominated by a single Slater determinant are described at the single-reference (SR) CCSD(T) level, whereas the lower-spin states, being inherently multiconfigurational in their nature, are treated with multireference (MR) methods, MRCI and\/or CASPT2. An original technique which scales MR results against SR CCSD(T) ones to improve the accuracy in the former is proposed and examined, taking the example of 12 electronic states of gadolinium monoxide, X9\u03a3\u2212, Y7\u03a3\u2212, A\u20329\u0394, A1\u20327\u0394, A9\u03a0, A17\u03a0, B9\u03a3\u2212, B17\u03a3\u2212, C9\u03a0, C17\u03a0, D9\u03a3\u2212, and D17\u03a3\u2212, up to 35\u2009000\u00a0cm\u22121. A multitude of the corresponding \u03a9 (spin-coupled) states was then studied within the state-interacting approach employing the full Breit\u2013Pauli spin\u2013orbit coupling operator with CASSCF-generated \u039bS states as a basis. For all \u039bS and \u03a9 states, the Gd\u2013O bond lengths, spectroscopic constants \u03c9e, \u03c9exe, \u03b1e, and adiabatic excitation energies are obtained. The theoretical predictions are in good agreement with the experimental data, with deviations in excitation energies not exceeding 350\u00a0cm\u22121 (1 kcal\/mol). The spectroscopic properties of the yet unobserved electronic states, A\u20329\u0394, A1\u20327\u0394, C9\u03a0, C17\u03a0, D9\u03a3\u2212, and D17\u03a3\u2212, are evaluated for the first time.<\/jats:p>","DOI":"10.1063\/5.0173916","type":"journal-article","created":{"date-parts":[[2023,10,25]],"date-time":"2023-10-25T06:17:01Z","timestamp":1698214621000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":0,"title":["A route to high-accuracy\n                    <i>ab\u00a0initio<\/i>\n                    description of electronic excited states in high-spin lanthanide-containing species: A case study of GdO"],"prefix":"10.1063","volume":"159","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-3792-734X","authenticated-orcid":false,"given":"Alexander N.","family":"Smirnov","sequence":"first","affiliation":[{"name":"Department of Physics, Ivanovo State University of Chemistry and Technology , Ivanovo 153000, Russia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1185-7213","authenticated-orcid":false,"given":"Victor G.","family":"Solomonik","sequence":"additional","affiliation":[{"name":"Department of Physics, Ivanovo State University of Chemistry and Technology , Ivanovo 153000, Russia"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"317","published-online":{"date-parts":[[2023,10,25]]},"reference":[{"key":"2023102714235670300_c1","doi-asserted-by":"publisher","first-page":"5803","DOI":"10.1063\/1.455556","volume":"89","year":"1988","journal-title":"J. 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