Multiple configurations of the two excess 4f electrons on defective CeO2(111):Origin and implications

Density-functional theory calculations have been carried out to systematically study single surface oxygen vacancies on CeO2(111). It is surprisingly found that multiple structures with the two excess electrons localized at different positions can exist. We show that the origin of the multiconfigurations of 4f electrons is a result of geometric relaxation on the surface and strong localization characteristic of 4f electrons in ceria. The importance of 4f electron structures is also presented and discussed. These results may possess implications for our understanding of materials with f electrons.

A density functional theory study of CO and atomic oxygen chemisorption on Pt(111)

Ab initio total energy calculations within a density functional theory framework have been performed for CO and atomic oxygen chemisorbed on the Pt(111) surface. Optimised geometries and chemisorption energies for CO and O on four high-symmetry sites, namely the top, bridge, fee hollow and hcp hollow sites, are presented, the coverage in all cases being 0.25 ML. The differences in CO adsorption energies between these sites are found to be small, suggesting that the potential energy surface for CO diffusion across Pt(111) is relatively flat. The 5 sigma and 2 pi molecular orbitals of CO are found to contribute to bonding with the metal. Some mixing of the 4 sigma and 1 pi molecular orbitals with metal states is also observed. For atomic oxygen, the most stable adsorption site is found to be the fee hollow site, followed in decreasing order of stability by the hcp hollow and bridge sites, with the top site being the least stable. The differences in chemisorption energies between sites for oxygen are larger than in the case of CO, suggesting a higher barrier to diffusion for atomic oxygen. The co-adsorption of CO and O has also been investigated. Calculated chemisorption energies for CO on an O/fcc-precovered surface show that of the available chemisorption sites, the top site at the oxygen atom's next-nearest neighbour surface metal atom is the most stable, with the other four sites calculated bring at least 0.29 eV less stable. The trend of CO site stability in the coadsorption system is explained in terms of a 'bonding competition' model. (C) 2000 Elsevier Science B.V. All rights reserved.

A first principles study of CH3 dehydrogenation on Ni(111)

Density functional theory with gradient corrections and spin polarization has been used to study the dehydrogenation of CH3 on Ni(111), a crucial step in many important catalytic reactions. The reaction, CH3(ads)--> CH2(ads)+H-(ads), is about 0.5 eV endothermic with an activation energy of more than 1 eV. The overall reaction pathway is rather intriguing. The C moiety translates from a hcp to a fcc site during the course of the reaction. The transition state of the reaction has been identified. The CH3 species is highly distorted, and both C and the active H are centered nearly on top of a row of Ni atoms with a long C-H bond length of 1.80 Angstrom. The local density of states coupled with examination of the real space distribution of individual quantum states has been used to analyze the reaction pathway. (C) 2000 American Institute of Physics. [S0021-9606(00)30218-5].

A density functional theory study of CH2 and H adsorption on Ni(111)

Ab initio total energy calculations within the density functional theory framework have been used to study the adsorption of CH2 and H as well as the coadsorption of CH2 and H on Ni(111). H binds strongly at threefold hollow sites with calculated adsorption energies of 2.60 and 2.54 eV at the face-centered-cubic (fcc) and hexagonal-close-packed (hcp) hollow sites, respectively. Adsorption energies and H-Ni distances are found to agree well with both experimental and theoretical results. CH2 adsorbs strongly at all high symmetry sites with calculated adsorption energies of 3.26, 3.22, 3.14 and 2.36 eV at the fcc, hcp, bridge and top sites, respectively. Optimized structures are reported at all sites, and, in the most stable hollow sites there is considerable internal reorganization of the CH2 fragment. The CH2 molecule is tilted, the hydrogens are inequivalent and the C-H bonds are lengthened relative to the gas phase. In the CH2-H coadsorption systems the adsorbates have a tendency to move toward bridge sites. The bonding of all adsorbates to the surface is analyzed in detail. (C) 2000 American Institute of Physics. [S0021-9606(00)71213-X].

Methyl chemisorption on Ni(111) and C-H-M multicentre bonding:a density functional theory study

Density functional theory has been used to study the adsorption of CH3 on Ni(111). CH3 is found to adsorb strongly at all four high symmetry sites of the Ni(111) surface. Calculated adsorption energies of CH3 on the different sites are in the following order: hcp approximate to fcc>bridge>top. The bonding and structures of CH3 on the different sites are analysed in detail. An important factor, namely three-centre bonding between carbon, hydrogen and nickel which contributes to the 'soft' C-H vibrational frequency of CH3 on Ni(111), and may determine the preferred chemisorption site, is stressed. (C) 1999 Elsevier Science B.V. All rights reserved.

Density functional theory study of the interaction between CO and on a Pt surface:CO/Pt(111), O/Pt(111), and CO/O/Pt(111)

Ab initio total energy calculations within the Density Functional Theory framework were carried out for Pt(111), Pt(111)-p(2x2)-CO, Pt(111)-p(2x2)-O, and Pt(111)-p(2x2)-(CO+O) to provide an insight into the interaction between CO and O on metal surfaces, an important issue in CO oxidation, and also in promotion and poisoning effects of catalysis. The geometrical structures of these systems were optimized with respect to the total energy, the results of which agree with existing experimental values very well. It is found that (i) the local structures of Pt(111)-p(2x2)-(CO+O), such as the bond lengths of C-O, C-Pt, and O-Pt (chemisorbed O atom with Pt), are almost the same as that in Pt(111)-p(2x2)-CO and Pt(111)-p(2x2)-O, respectively, (ii) the total valence charge density distributions in Pt(111)-p(2x2)-(CO+O) are very similar to that in Pt(111)-p(2x2)-CO, except in the region of the chemisorbed oxygen atom, and also nearly identical to that in Pt(111)-p(2x2)-O, apart from in the region of the chemisorbed CO, and (iii) the chemisorption energy of CO on a precovered Pt(111)-p(2x2)-O and the chemisorption energy of O on a precovered Pt(111)-p(2x2)CO are almost equal to that in Pt(111)-p(2x2)-CO and Pt(111)-p(2x2)-O, respectively. These results indicate that the interaction between CO and chemisorbed oxygen on a metal surface is mainly shore range in nature. The discussions of Pt-CO and Pt-O bonding and the interaction between CO and the chemisorbed oxygen atom on Pt(111) are augmented by local densities of states and real space distributions of quantum states.

A density functional theory study on the interaction between chemisorbed CO and S on Rh(111)

Density functional theory calculations are carried out for Rh(111)-p(2 x 2)-CO, Rh(111)-p(2 x 2)-S, Rh(111)-p(2 x 2)-(S + CO), Rh(111)-p(3 x 3)-CO, Rh(111)-p(3 x 3)-S and Rh(111)-p(3 x 3)-(S + CO), aiming to shed some light on the S poisoning effect. Geometrical structures of these systems are optimized and chemisorption energies are determined. The presence of S does not significantly influence the geometrical structure and chemisorption energy of CO and vice versa, which strongly suggests that the interaction between CO and S on the Rh(111) surface is mainly short-range in nature. The long range electronic effect for the dramatic attenuation of the CO methanation activity by sulfur is likely to be incorrect. It is suggested that an ensemble effect may be dominant in the catalytic deactivation. (C) 1999 Elsevier Science B.V. All rights reserved.

CO oxidation on Pt(111):An ab initio density functional theory study

CO oxidation on Pt(111) is studied with ab initio density functional theory. The low energy pathway and transition state for the reaction are identified. The key event is the breaking of an O-metal bond prior to the formation of a chemisorbed CO2 molecule. The pathway can be rationalized in terms of competition of the O and C atoms for bonding with the underlying surface, and the predominant energetic barrier is the strength of the O-metal bond.