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Theoretical studies on the structures and electronic spectra of carbon chains C n N (n = 3–12)

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Abstract

A theoretical study of the linear nitrogen-terminated carbon chains C n N (n = 3–12) is carried out with density functional theories and ab initio methods. All species in the ground state are fully optimized with the B3LYP, CAM-B3LYP, and RCCSD(T) calculations. The present results reveal that the carbon radicals under study possess stable structures with the X 2Σ+ ground-state symmetry for C n N (n = 3, 5) or X 2Π for the rest members in the series. According to the trends of odd/even alternation in energy differences and incremental binding energies, it is clear that the n-odd C n N chains are relatively more stable than n-even ones. Furthermore, the electronic spectra of C n N (n = 3–12) are investigated by means of CASPT2 method. The predicted vertical excitation energies from the ground state to the low-lying excited states basically agree well with the available experimental observations. In addition, by performing curve fittings, the vertical excitation energies of the transitions from the ground states (X 2Σ+ or X 2Π) to the low-lying excited state 22Π for the odd members are found to obey a nonlinear ΔE–n relationship as a function of chain size, matching the experimental findings well. Moreover, the strongest absorption band for the even series shows a nonlinear trend of biexponential decay.

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Acknowledgments

The authors gratefully thank the State Key Laboratory of Physical Chemistry of Solid Surfaces of Xiamen University for providing computational resources. This work was supported by the National Natural Science Foundation of China (21003036), the Foundation for University Key Teachers from the He’nan Educational Committee, Science Foundation of He’nan Educational Committee (2008A150005 and 2011B150003), Science Foundation of Henan University (SBGJ090507), and Doctor Foundation of Henan University.

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  1. Institute of Environmental and Analytical Sciences, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, 475004, China

    Yanxin Zhang, Yuanyuan Li, Li Wang & Jinglai Zhang

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  1. Yanxin Zhang
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  2. Yuanyuan Li
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  3. Li Wang
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Correspondence to Jinglai Zhang.

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Zhang, Y., Li, Y., Wang, L. et al. Theoretical studies on the structures and electronic spectra of carbon chains C n N (n = 3–12). Theor Chem Acc 133, 1420 (2014). https://doi.org/10.1007/s00214-013-1420-2

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