Carbon dioxide activation by y atom and y+ cation in the gas phase: A density functional theoretical study

• DE-MAN HAN ^[1] ; GUO-LIANG DAI ^[1] ; ZHEN-ZHONG YAN ^[1] ; CHUAN-FENG WANG ^[1] ; AI-GUO ZHONG ^[1]
  1. [1] Taizhou University

     Taizhou University

     China

     
• Localización: Journal of the Chilean Chemical Society (Boletín de la Sociedad Chilena de Química), ISSN-e 0717-6309, ISSN 0366-1644, Vol. 55, Nº. 1, 2010, págs. 121-125
• Idioma: inglés
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• Resumen

  • The potential energy surfaces for the Y+CO2 and Y++CO2 reactions have been investigated by using the DFT (B3LYP/ECP/6-31 l+G*) level of theory. Both ground and excited state potential energy surfaces are discussed. The present results show that the reaction mechanism is an insertion mechanism along the C-O bond activation branch. The reaction of Y atom with CO2 was shown to occur preferentially on the doublet PES throughout the reaction process. As for the reaction between Y+cation with CO2, it involves potential energy curve-crossing which dramatically affects reaction mechanism. Due to the intersystem crossing existing in the reaction process of Y+with CO2, the intermediate (OY(η2CO))+ may not form. This mechanism is different from that of Y + CO2 system. All our theoretical results not only support the existing conclusions inferred from early experiment, but also complement the pathway and mechanism for this reaction.