{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,2,19]],"date-time":"2026-02-19T18:34:05Z","timestamp":1771526045977,"version":"3.50.1"},"reference-count":63,"publisher":"AIP Publishing","issue":"15","content-domain":{"domain":["pubs.aip.org"],"crossmark-restriction":true},"short-container-title":[],"published-print":{"date-parts":[[2007,10,21]]},"abstract":"<jats:p>The observation of several metal cyanides and isocyanides in interstellar space has raised much interest these molecules. Optimum molecular structures, harmonic vibrational frequencies, and dipole moments of the ground electronic states (X\u0303\u03a3+1), triplet excited states, and open shell singlet excited states of CuCN and CuNC were determined using different levels of nonrelativistic and scalar relativistic (Douglas-Kroll) [Ann. Phys.\u200882, 89 (1979)] coupled cluster theory in conjunction with atomic natural orbital basis sets and correlation consistent basis sets. For the relativistic computations the specially contracted correlation consistent Douglas-Kroll (DK) basis sets were used. Moreover, barriers to isomerization from CuCN to CuNC were computed. The predicted structures of the X\u0303\u03a3+1 state for CuCN are re(Cu\u2013C)=1.826\u00c5 and re(C\u2013N)=1.167\u00c5, at the most sophisticated level of theory, the scalar relativistic DK-CCSD(T)\/cc-pVQZ(DK) method. These results are in excellent agreement with the experimentally determined Cu\u2013C bond length of 1.829\u00c5 and C\u2013N bond distance of 1.162\u00c5. At the same level of theory, the zero-point corrected barrier to isomerization from CuCN to CuNC is estimated to be 14.7kcalmol\u22121, and the cyanide is more stable than the isocyanide by 11.5kcalmol\u22121. For both CuCN and CuNC the \u03a3+3 state is the lowest lying excited electronic state. At the DK-CCSD\/cc-pVQZ(DK) level of theory, the energetic ordering of excited states of CuCN and CuNC is X\u0303\u03a3+1&amp;lt;a\u0303\u03a3+3&amp;lt;b\u0303\u03a03&amp;lt;2\u03a3+1\u2248\u03943&amp;lt;\u03a01&amp;lt;\u03941. The variations of CN bond lengths in the optimized structures for the different electronic states and the CN stretching frequencies of the ground state and the excited states suggest that metal d\u03c0 to ligand \u03c0 charge transfer is insignificant, in contrast to previous results for isoelectronic NiCO.<\/jats:p>","DOI":"10.1063\/1.2784393","type":"journal-article","created":{"date-parts":[[2007,10,19]],"date-time":"2007-10-19T20:47:49Z","timestamp":1192826869000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":7,"title":["Coupled cluster investigation on the low-lying electronic states of CuCN and CuNC and the ground state barrier to isomerization"],"prefix":"10.1063","volume":"127","author":[{"given":"Ankan","family":"Paul","sequence":"first","affiliation":[{"name":"University of Georgia Center for Computational Chemistry, , Athens, Georgia 30602, USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Yukio","family":"Yamaguchi","sequence":"additional","affiliation":[{"name":"University of Georgia Center for Computational Chemistry, , Athens, Georgia 30602, USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"suffix":"III","given":"Henry F.","family":"Schaefer","sequence":"additional","affiliation":[{"name":"University of Georgia Center for Computational Chemistry, , Athens, Georgia 30602, USA"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"317","published-online":{"date-parts":[[2007,10,19]]},"reference":[{"key":"2023073121503984100_c1","doi-asserted-by":"publisher","first-page":"6933","DOI":"10.1021\/ja015948n","volume":"123","year":"2001","journal-title":"J. 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