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Title: Ab initio investigation of high multiplicity Σ⁺"⁻"Σ⁺ optical transitions in the spectra of CN and isoelectronic species

Abstract

Due to high-level ab initio calculations, we predict the existence of a strong 4Σ⁺"⁻"Σ⁺ optical transition (d av=1.6 D) near 328 nm (T 00 = 30 460 cm –1), analogous to the B 2Σ⁺"⁻"X 2Σ⁺ violet system, (d av=1.7 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 quasibound (r e=1.76 Å, ω e = 365 cm –1) , and a 6Σ⁺"⁻" 6Σ⁺ transition, analogous to those for the doublet and quartet multiplicities, is predicted (d av=2.2 D). Investigation of the isoelectronic BO, C$$^{–}_{2}$$, and N$$^{+}_{2}$$ molecules reveals that differences in 2s 22p x and 2s 12p x+1 atomic energies play the key role in determining the magnitude of the 5σ(2p)←4σ(2s)-derived Σ⁺"⁻"Σ⁺ transition energies for the different multiplets. Furthermore, the strong stabilization of 2s 22p x character with respect to 2s 12p x+1 in BO and N$$^{+}_{2}$$ leads to strongly bound lowest 6Σ⁺ states with binding energies as high as 2.0 eV. We think that these newly predicted sextet states could be identified through their perturbations of quartet states of the relevant molecules.

Authors:
 [1];  [1];  [1]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Publication Date:
Research Org.:
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1557817
Grant/Contract Number:  
FG02-87ER13671
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Molecular Spectroscopy
Additional Journal Information:
Journal Volume: 258; Journal Issue: 1-2; Journal ID: ISSN 0022-2852
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Cyanide; Ab initio; Electronic spectrum; Quartet states

Citation Formats

Kulik, Heather J., Steeves, Adam H., and Field, Robert W. Ab initio investigation of high multiplicity Σ⁺"⁻"Σ⁺ optical transitions in the spectra of CN and isoelectronic species. United States: N. p., 2009. Web. doi:10.1016/j.jms.2009.08.008.
Kulik, Heather J., Steeves, Adam H., & Field, Robert W. Ab initio investigation of high multiplicity Σ⁺"⁻"Σ⁺ optical transitions in the spectra of CN and isoelectronic species. United States. doi:10.1016/j.jms.2009.08.008.
Kulik, Heather J., Steeves, Adam H., and Field, Robert W. Sat . "Ab initio investigation of high multiplicity Σ⁺"⁻"Σ⁺ optical transitions in the spectra of CN and isoelectronic species". United States. doi:10.1016/j.jms.2009.08.008. https://www.osti.gov/servlets/purl/1557817.
@article{osti_1557817,
title = {Ab initio investigation of high multiplicity Σ⁺"⁻"Σ⁺ optical transitions in the spectra of CN and isoelectronic species},
author = {Kulik, Heather J. and Steeves, Adam H. and Field, Robert W.},
abstractNote = {Due to high-level ab initio calculations, we predict the existence of a strong 4Σ⁺"⁻"Σ⁺ optical transition (dav=1.6 D) near 328 nm (T00 = 30 460 cm–1), analogous to the B2Σ⁺"⁻"X2Σ⁺ violet system, (dav=1.7 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 quasibound (re=1.76 Å, ωe = 365 cm–1) , and a 6Σ⁺"⁻"6Σ⁺ transition, analogous to those for the doublet and quartet multiplicities, is predicted (dav=2.2 D). Investigation of the isoelectronic BO, C$^{–}_{2}$, and N$^{+}_{2}$ molecules reveals that differences in 2s22px and 2s12px+1 atomic energies play the key role in determining the magnitude of the 5σ(2p)←4σ(2s)-derived Σ⁺"⁻"Σ⁺ transition energies for the different multiplets. Furthermore, the strong stabilization of 2s22px character with respect to 2s12px+1 in BO and N$^{+}_{2}$ leads to strongly bound lowest 6Σ⁺ states with binding energies as high as 2.0 eV. We think that these newly predicted sextet states could be identified through their perturbations of quartet states of the relevant molecules.},
doi = {10.1016/j.jms.2009.08.008},
journal = {Journal of Molecular Spectroscopy},
number = 1-2,
volume = 258,
place = {United States},
year = {2009},
month = {8}
}

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