Acta Phys. -Chim. Sin. ›› 2010, Vol. 26 ›› Issue (05): 1378-1384.doi: 10.3866/PKU.WHXB20100523

• QUANTUM CHEMISTRY AND COMPUTATION CHEMISTRY • Previous Articles     Next Articles

CO Adsorption on α-U(001) Surface

LI Gan, LUO Wen-Hua, CHEN Hu-Chi   

  1. National Key Laboratory for Surface Physics and Chemistry, Mianyang 621907, Sichuan Province, P. R. China; China Academy of Engineering Physics, Mianyang 621900, Sichuan Province, P. R. China
  • Received:2009-10-26 Revised:2010-01-19 Published:2010-04-29
  • Contact: LI Gan E-mail:2002ligan@sina.com

Abstract:

The adsorption, dissociation, and diffusion of CO on the α-U(001) surface were studied using density functional theory with the generalized gradient approximation (GGA). The calculation results show that a CU3OU2-type molecular chemisorption of CO is favored with adsorption energies of 1.78-1.99 eV. The U atoms of the surface layer are found to move upwards after adsorption coupled with a rumpling of the surface layer. The interaction between the U atoms and a CO molecule results mainly from the population of the CO 2π* LUMO by U electrons and the CO 2π*/5σ/1π-U 6d orbital hybridization. Dissociative adsorption is energetically more favored than molecular adsorption with adsorption energies of 2.71 and 3.08 eVfor the h1(C)+h2(O) and h1(C)+h1(O) (h: hollowsite) dissociative configurations, respectively. The diffusion barriers of C and O atoms between two adjacent threefold hollow sites are found to be 0.57 and 0.14 eV, respectively, which indicates that the on-surface diffusion ofO atoms is more easily achieved than that of C atoms.

Key words: Density functional theory, α-U(001) surface, Carbon monoxide, Adsorption

MSC2000: 

  • O641