Acta Phys. -Chim. Sin. ›› 2013, Vol. 29 ›› Issue (11): 2308-2312.doi: 10.3866/PKU.WHXB201309042

• THEORETICAL AND COMPUTATIONAL CHEMISTRY • Previous Articles     Next Articles

Density Functional Theory Study of the Gas-Phase Reaction of U+ with CO2

ZENG Xiu-Lin1,2, HUANG Shan-Qi-Song2, JU Xue-Hai2   

  1. 1 Department of Chemistry and Chemical Engineering, Huainan Normal University, Huainan 232001, Anhui Province, P. R. China;
    2 Department of Chemistry, Nanjing University of Science and Technology, Nanjing 210094, P. R. China
  • Received:2013-05-15 Revised:2013-09-04 Published:2013-10-30
  • Contact: JU Xue-Hai E-mail:xhju@mail.njust.edu.cn
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (21101070).

Abstract:

The gas-phase reaction of U+ with CO2 was investigated with B3LYP density functional theory (DFT) in conjunction with the relativistic effective core potential (ECP) of the SDD basis sets for Uand the 6-311 + G(d) basis set for C and O. The potential energy surfaces (PESs) of the reaction system were explored in detail for both doublet and quartet spin states. The geometries of reactants, intermediates, transition states, and products in the two reaction pathways were fully optimized. The reaction mechanism was analyzed using"two-state reactivity (TSR)."The calculations demonstrate that the reaction preferentially involves the high-spin state entrance channel and the low-spin state exit channel. The spin multiplicity transition from the quartet state to the doublet state enables the reaction system to find a lower energy pathway.

Key words: Reaction mechanism, Density functional theory, Relativistic effective core potential, Potential energy surface, Spin state

MSC2000: 

  • O641