The ground state structure for the CCCCCl radical was computed by using symmetry-adapted cluster configuration-interaction (SAC-CI) theory along with density functional theory to overcome the differences raised in the recently published paper [Y. Sumiyoshi et al, Chem. Phys. Lett. 414, 82 (2005)] between the theory and the experiment. SAC-CI results clearly support the earlier experimental conclusion that the radical has the bent ground state structure corresponding to symmetry. Contrarily, probably due to spin contamination, mixing of a bent doublet ground state with the quartet components of a linear structure, coupled-cluster singles and doubles (CCSD) calculations were unable to provide reliable results. Results obtained using density functional theory also show that the radical has a bent structure. Some low-lying doublet excited states were also studied using the SAC-CI theory. The energy difference between the ground state and the nearby state is around . The excitation energy for the transition with the largest oscillator strength agrees with the strongest absorption peak.
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Research Article| November 17 2006
: Bent or linear?
Hiroshi Nakatsuji a)
Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering,
Kyoto University, Katsura, Nishikyou-ku, Kyoto 615-8510, Japan and Fukui Institute for Fundamental Chemistry,
Kyoto University, 34-4 Takano, Nishihiraki-cho, Sakyo-ku, Kyoto 606-8103, Japan
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Sundaram Arulmozhiraja, Masahiro Ehara, Hiroshi Nakatsuji; : Bent or linear?. J. Chem. Phys. 21 November 2006; 125 (19): 194314. https://doi.org/10.1063/1.2393224
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