Theory of orthogonal interactions of CO molecules on a one-dimensional substrate

Abstract

A minimal model based on density functional theory is proposed and solved to explain the unusual chemisorption properties of carbon-monooxide (CO) molecules on Cu (110) (1) the strong lifting of the host Cu atom by 1Å, and (2) the highly anisotropic CO-CO interaction leading to self-assembly into a nano-grating structure. Our model implies the 1D nature of the surface band is the key to these two features. We illustrate how formation of a chemical bond through specific orbital interactions between an adsorbate and 1D dispersive states of the substrate can impact the surface geometrical and electronic structure.

Self-Catalyzed Carbon Dioxide Adsorption by Metal–Organic Chains on Gold Surfaces

“…Furthermore, adsorbate diffusion can be highly anisotropic, for example restricting the motion predominantly along the 1D chains. In the case of CO chemisorption on Cu(110)-2 × 1-O added row surface, we have shown how the particular properties of 1D molecular chains enable anisotropic 1D self-assembly of CO molecules into molecular grating structures that seemingly contradict the well-established characteristics of CO adsorption on 2D metal surfaces. ,, …”

“…1D surfaces enable strong adsorbate–substrate interactions as well as adsorption-induced cooperative phenomena that are more pronounced than for the less mutable 2D surfaces . The primary example of 1D surfaces are noble metal–oxygen atom added row structures on Cu(110) and Ag(110) surfaces. − These added row structures exhibit 1D electronic structures, strong correlation in the Cu(Ag)–O chain separations, low coordination of metal atoms that enables high structural flexibility toward interaction with adsorbates, and chemical properties that are intermediate between those of molecules and 2D surfaces. ,,, The structure and dimensionality of 1D surfaces necessitates strongly anisotropic interactions, which promotes adsorbate correlation. , For example, adsorption of one molecule on a 1D chain can promote or poison further adsorption in the proximity of the primary site. Furthermore, adsorbate diffusion can be highly anisotropic, for example restricting the motion predominantly along the 1D chains.…”

“…14À19 These added row structures exhibit 1D electronic structures, strong correlation in the Cu(Ag)ÀO chain separations, low coordination of metal atoms that enables high structural flexibility toward interaction with adsorbates, and chemical properties that are intermediate between those of molecules and 2D surfaces. 13,16,20,21 The structure and dimensionality of 1D surfaces necessitates strongly anisotropic interactions, which promotes adsorbate correlation. 13,22 For example, adsorption of one molecule on a 1D chain can promote or poison further adsorption in the proximity of the primary site.…”

“…In the case of CO chemisorption on Cu(110)-2 Â 1-O added row surface, we have shown how the particular properties of 1D molecular chains enable anisotropic 1D self-assembly of CO molecules into molecular grating structures that seemingly contradict the well-established characteristics of CO adsorption on 2D metal surfaces. 13,20,21 Strongly electron withdrawing organic molecules can extract atoms from metal substrates to selforganize into highly structured surface metalÀorganic compounds. 23À28 Although 2D metalÀorganic compounds can have novel interactions with adsorbates, 29 they lack the structural flexibility, which enables 1D MOCs to respond to chemical stimulation.…”

Temperature-Controlled CO Adsorption Configurations on (2 × 1)Ni–O/Ni(110) Surfaces

“…Such a chain-like CO adsorption mode was also observed on (2 × 1)Cu−O/ Cu(110) surfaces. 33,34 At 1/2 ML, the calculated VF shifts to 2068 cm −1 (Figure 3c), corresponding to the 2119 cm −1 band in IR spectra. Furthermore, the calculated frequency shift (10 cm -1 , 2058−2068 cm −1 ) with respect to CO coverage is in very good agreement with that of IRRAS results (9 cm -1 , 2110−2119 cm −1 ) for CO adsorption at 90 K.…”