ELECTRONIC GROUND AND EXCITED STATES OF CoN: AN AB INITIO MOLECULAR ORBITAL STUDY

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2003

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Ohio State University

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Based on the information from Tanaka group of Hokkaido University,$^{a}$ we have studied the $^{1}\Sigma^{+}$ and $^{5}\Delta$ states of CoN by ab initio molecular orbital methods as an extension of our previous work on FeN.$^{b}$ The $MR-SDCI+Q+E_{rel}$/[Roos ANO(Co), aug-cc-pVQZ(N)] $calculations^{c}$ with full-valence plus Co $3_{s}$ and $3_{p}$ electron correlations predicted that the $^{5}\Delta$ level should be located by about $4300 cm^{-1}$ higher than the $^{1}\Sigma^{+}$ state. Hence, the electronic ground state is $^{1}\Sigma^{+}$. The equilibrium bond lengths for the $^{1}\Sigma^{+}$ and $^{5}\Delta$ states at this level of calculation are 1.5621 and $1.5945 {\AA}$, respectively. The first order relativistic correction $E_{rel}$ increases linearly with the Co-N bond length, with steeper gradient for $^{1}\Sigma^{+}$ than $^{5}\Delta$ states as is expected. The resultant shortening of the Co-N bond due to the relativistic effect is 0.016 and $0.005 {\AA}$ for the $^{1}\Sigma^{+}$ and $^{5}\Delta$ states, respectively.

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$^{a}$ K. Tanaka and M. Sekiya, Division of Chemistry, Graduate School of Science, Hokkaido University, Sapporo 060-0808, Japan. $^{b}$ M. Amano, S.S Itono, T. Hirano, U. Nagashima, M. Sekiya, and K. Tanaka, The 57th Ohio State University International Symposium on Molecular Spectroscopy, FB06, 255 (2002) $^{c}$ Q: Davidson's correction; $E_{rel}$: Relativistic correction
Author Institution: Grid Technology Research Center, Institute of Advanced Industrial Science and Technology

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