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Ab initio investigation of high multiplicity Rþ—Rþ [sigma superscript + - sigma superscript +] optical transitions in the spectra of CN and isoelectronic species

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dc.contributor.author Kulik, Heather J.
dc.contributor.author Steeves, Adam H.
dc.contributor.author Field, Robert W.
dc.date.accessioned 2011-09-21T18:29:46Z
dc.date.available 2011-09-21T18:29:46Z
dc.date.issued 2009-08
dc.date.submitted 2009-07
dc.identifier.issn 0022-2852
dc.identifier.uri http://hdl.handle.net/1721.1/65911
dc.description.abstract Based on high-level ab initio calculations, we predict the existence of a strong 4Σ+–4Σ+ [superscript 4 sigma superscript + - superscript 4 sigma superscript +] optical transition (dav=1.6 D) [(d subscript av = 1.6 D)] near 328 nm (T00 = 30460 cm-1) [(T subscript 00 = 30460 cm superscript -1)], analogous to the B 2Σ+ - X 2Σ+ [B superscript 2 sigma superscript + - X superscript 2 sigma superscript +] violet system, (dav=1.7 D) [(d subscript av = 2.2 D)] in the near-ultraviolet spectrum of CN. The lower state of the predicted transition is the lowest-lying state of quartet multiplicity and has been observed previously through its perturbations of the B state. The predicted transition will enable determination of the equilibrium properties of the metastable lowest quartet state of CN. The lowest energy metastable sextet state of CN is also calculated to be quasi-bound (re=1.76 A, we = 365 cm-1) [(r subscript e = 1.76 angstrom, omega subscript e = 365 cm superscript -1)], and a 6Σ+–6Σ+ [superscript 6 sigma superscript + - superscript 6 sigma superscript +] transition, analogous to those for the doublet and quartet multiplicities, is predicted (dav=2.2 D) [(d subscript av = 2.2 D)]. Investigation of the isoelectronic BO, C-2 [C subscript 2 superscript -], and N+2 [N subscript 2 superscript +] molecules reveals that differences in 2s22px [2s superscript 2 2p superscript x] and 2s12px+1 [2s superscript 1 2p superscript x+1] atomic energies play the key role in determining the magnitude of the 5σ(2p)←4σ(2s)-derived [5 sigma (2p)← 4 sigma (2s)-derived] Σ+–Σ+ [sigma superscript + - sigma superscript +] transition energies for the different multiplicities. Furthermore, the strong stabilization of 2s22px [2s superscript 2 2p superscript x] character with respect to 2s12px+1 [2s superscript 1 2p superscript x+1] in BO and N+2 [N subscript 2 superscript +] leads to strongly bound lowest 6Σ+ [superscript 6 sigma superscript +] states with binding energies as high as 2.0 eV. We believe that these newly predicted sextet states could be identified through their perturbations of quartet states of the relevant molecules. en_US
dc.description.sponsorship National Science Foundation (U.S.) en_US
dc.description.sponsorship United States. Dept. of Energy (Grant DE-FG0287ER13671) en_US
dc.language.iso en_US
dc.publisher Elsevier ScienceDirect en_US
dc.relation.isversionof http://dx.doi.org/10.1016/j.jms.2009.08.008 en_US
dc.rights Creative Commons Attribution-Noncommercial-Share Alike 3.0 en_US
dc.rights.uri http://creativecommons.org/licenses/by-nc-sa/3.0/ en_US
dc.source Prof. Field via Erja Kajosalo en_US
dc.title Ab initio investigation of high multiplicity Rþ—Rþ [sigma superscript + - sigma superscript +] optical transitions in the spectra of CN and isoelectronic species en_US
dc.type Article en_US
dc.identifier.citation Kulik, Heather J., Adam H. Steeves, and Robert W. Field. “Ab Initio Investigation of High Multiplicity Σ+–Σ+Σ+–Σ+ Optical Transitions in the Spectra of CN and Isoelectronic Species.” Journal of Molecular Spectroscopy 258.1-2 (2009) : 6-12. Copyright © 2009, Elsevier en_US
dc.contributor.department Massachusetts Institute of Technology. Department of Materials Science and Engineering en_US
dc.contributor.department Massachusetts Institute of Technology. Department of Chemistry en_US
dc.contributor.department Massachusetts Institute of Technology. Spectroscopy Laboratory en_US
dc.contributor.approver Field, Robert W.
dc.contributor.mitauthor Kulik, Heather J.
dc.contributor.mitauthor Steeves, Adam H.
dc.contributor.mitauthor Field, Robert W
dc.relation.journal Journal of Molecular Spectroscopy en_US
dc.identifier.mitlicense OPEN_ACCESS_POLICY en_US
dc.eprint.version Author's final manuscript en_US
dc.type.uri http://purl.org/eprint/type/JournalArticle en_US
eprint.status http://purl.org/eprint/status/PeerReviewed en_US
dspace.orderedauthors Kulik, Heather J.; Steeves, Adam H.; Field, Robert W. en


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