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Spin-flip reactions of Zr + C2H6 researched by relativistic density functional theory

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Abstract

Density functional theory (DFT) with relativistic corrections of zero-order regular approximation (ZORA) has been applied to explore the reaction mechanisms of ethane dehydrogenation by Zr atom with triplet and singlet spin-states. Among the complicated minimum energy reaction path, the available states involves three transition states (TS), and four stationary states (1) to (4) and one intersystem crossing with spin-flip (marked by ⇒): 3Zr + C 2 H 6 → 3Zr-CH 3 -CH 3 (3 1) → 3 TS 1/2 → 3ZrH-CH 2 -CH 3 (3 2) → 3 TS 2/3 ⟹ 1ZrH2-CH2 = CH2 (1 3) → 1 TS 3/4 → 1ZrH 3 -CH = CH 2 (1 4). The minimum energy crossing point is determined with the help of the DFT fractional-occupation-number (FON) approach. The spin inversion leads the reaction pathway transferring from the triplet potential energy surface (PES) to the singlet’s accompanying with the activation of the second C-H bond. The overall reaction is calculated to be exothermic by about 231 kJ mol−1. Frequency and NBO analysis are also applied to confirm with the experimental observed data.

Reaction \( {}^{\mathbf{3}}\mathrm{Zr}+{\mathrm{C}}_{\mathbf{2}}{\mathrm{H}}_{\mathbf{6}}{\to}^{\mathbf{3}}\mathrm{Zr}\mathrm{H}-{\mathrm{C}\mathrm{H}}_{\mathbf{2}}-{\mathrm{C}\mathrm{H}}_{\mathbf{3}}{\Rightarrow}^{\mathbf{1}}{\mathrm{ZrH}}_2-{\mathrm{C}\mathrm{H}}_2={\mathrm{C}\mathrm{H}}_2{\to}^{\mathbf{1}}{\mathrm{ZrH}}_{\mathbf{3}}-\mathrm{CH}={\mathrm{C}\mathrm{H}}_{\mathbf{2}} \)proceeds via spin-flip surface hopping over several transition states has been investigated. The minimum energy crossing point is determined with the help of the DFT fractional-occupation-number (FON) approach.

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Acknowledgments

We acknowledge financial support by the National Nature Science Foundation of China (No. 20973109).

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  1. School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 200240, Shanghai, China

    Yi Xiao, Xian-Yang Chen, Yi-Xiang Qiu & Shu-Guang Wang

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  1. Yi Xiao
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Correspondence to Shu-Guang Wang.

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Xiao, Y., Chen, XY., Qiu, YX. et al. Spin-flip reactions of Zr + C2H6 researched by relativistic density functional theory. J Mol Model 19, 4003–4012 (2013). https://doi.org/10.1007/s00894-013-1932-7

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