Surface chemical reactivity of ultrathin Pd(111) films on Ru(0001): Importance of orbital symmetry in the application of the d-band model

Yin, Xiangshi; Cooper, Valentino R.; Weitering, Hanno H.; Snijders, Paul C.

doi:10.1021/acs.jpcc.5b06653

Title: Surface chemical reactivity of ultrathin Pd(111) films on Ru(0001): Importance of orbital symmetry in the application of the d-band model

Journal Article · Tue Sep 22 00:00:00 EDT 2015 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.5b06653· OSTI ID:1223666

Yin, Xiangshi ^[1]; Cooper, Valentino R. ^[2]; Weitering, Hanno H. ^[1]; Snijders, Paul C. ^[1]

Univ. of Tennessee, Knoxville, TN (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

The chemical bonding of adsorbate molecules on transition-metal surfaces is strongly influenced by the hybridization between the molecular orbitals and the metal d-band. The strength of this interaction is often correlated with the location of the metal d-band center relative to the Fermi level. Here, we exploit finite size effects in the electronic structure of ultrathin Pd(111) films grown on Ru(0001) to tune their reactivity by changing the film thickness one atom layer at a time, while keeping all other variables unchanged. Interestingly, while bulk Pd(111) is reactive toward oxygen, Pd(111) films below five monolayers are surprisingly inert. This observation is fully in line with the d-band model prediction when applied to the orbitals involved in the bonding. The shift of the d-band center with film thickness is primarily attributed to shifts in the partial density of states associated with the 4d_xz and 4d_yz orbitals. This study provides an in-depth look into the orbital specific contributions to the surface chemical reactivity, providing new insights that could be useful in surface catalysis.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1223666

Journal Information:: Journal of Physical Chemistry. C, Vol. 119, Issue 41; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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