CARBON DIOXIDE ACTIVATION BY Y ATOM AND Y+ CATION IN THE GAS PHASE: A DENSITY FUNCTIONAL THEORETICAL STUDY

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.

Bibliographic Details

Main Authors:	HAN,DE-MAN, DAI,GUO-LIANG, YAN,ZHEN-ZHONG, WANG,CHUAN-FENG, ZHONG,AI-GUO
Format:	Digital revista
Language:	English
Published:	Sociedad Chilena de Química 2010
Online Access:	http://www.scielo.cl/scielo.php?script=sci_arttext&pid=S0717-97072010000100029
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