Nature of Adsorption on TiC(111)

TL;DR

This study uses density-functional calculations to analyze atom adsorption on TiC(111), revealing strong chemisorption, electronic surface resonances, and proposing a model for understanding adsorption mechanisms relevant to technological applications.

Contribution

The paper introduces a concerted-coupling model based on electronic surface resonances to explain chemisorption on TiC surfaces, supported by detailed computational results.

Findings

Strong chemisorption for O atom at 8.8 eV

Presence of Ti-based and C-based surface resonances

Variation in adsorption energies with periodic trends

Abstract

Extensive density-functional calculations are performed for chemisorption of atoms in the three first periods (H, B, C, N, O, F, Al, Si, P, S, and Cl) on the polar TiC(111) surface. Calculations are also performed for O on TiC(001), for full O(1x1) monolayer on TiC(111), as well as for bulk TiC and for the clean TiC(111) and (001) surfaces. Detailed results concerning atomic structures, energetics, and electronic structures are presented. For the bulk and the clean surfaces, previous results are confirmed. In addition, new detailed results are given on the presence of C-C bonds in the bulk and at the surface, as well as on the presence of a Ti-based surface resonance (TiSR) at the Fermi level and of C-based surface resonances (CSR's) in the lower part of the surface upper valence band (UVB). For the adsorption, adsorption energies E_ads and relaxed geometries are presented, showing great variations characterized by pyramid-shaped E_ads trends within each period. An extraordinarily strong chemisorption is found for the O atom, 8.8 eV/adatom. On the basis of the calculated electronic structures, a concerted-coupling model for the chemisorption is proposed, in which two different types of adatom-substrate interactions work together to provide the obtained strong chemisorption: (i) adatom-TiSR and (ii) adatom-CSR's. This model is used to successfully describe the essential features of the calculated E_ads trends. The fundamental nature of this model, based on the Newns-Anderson model, should make it apt for general application to transition-metal carbides and nitrides, and for predictive purposes in technological applications, like cutting-tool multilayer coatings and MAX phases.