First-Principle Study of Adsorption and Desorption of Chlorine on Cu(111) Surface: Does Chlorine or Copper Chloride Desorb?

Abstract

First-principle density-functional calculations have been applied to study the interaction of molecular chlorine with the (111) plane of copper. Using transition-state search method, we considered the elementary processes (Cl2 dissociation, adsorption, diffusion, association and desorption) on the chlorinated Cu(111) surface. A systematic study of possible desorption pathways has been carried out for different species (Cl, Cl2, CuCl, CuCl2, and Cu) at various chlorine coverage. As a result, we concluded that chlorine monolayer irrespective of the coverage desorbs in the form of CuCl molecules from step edges.

First-Principles Study of Chlorine Adsorption on Clean Al(111)

“…Density functional theory (DFT) 10) is a powerful theoretical tool for elucidating the chemical nature of materials on the atomic scale. Many DFT investigations have been published on the surface structure of halogen adsorption onto a metal surface, especially for noble metals [11][12][13][14][15][16][17][18][19][20][21][22][23][24][25] . Optimization of the adsorption structures of Cl − , Br − , and I − as well as their harmonic vibration frequencies on the (100) surface of Cu, Ag, and Au have been studied by Ignaczak and Gomes 17) .…”

“…In addition, the energetics, electronic structure, and vibrational frequency of F, Cl, Br, and I adsorption onto the (111) surface of Cu, Rh, Pd, Ag, Pt, and Au have been investigated by Migani and Illas 19) . The chlorine adsorption and desorption mechanisms and the electronic structure of chlorine on Cu(111) have been investigated in detail by Peljhan and Kokalj 24) and by Pavlova et al 21) Few studies have focused on chlorine adsorption onto an aluminum surface. Mitsutake et al showed that the dissociative adsorption of Cl 2 molecules on Al(100) proceeds spontaneously with its bonding being ionic 26) .…”

A first principles kinetic Monte Carlo investigation of the adsorption and mobility of gadolinium on the (100) surface of tungsten

“…Next, we calculated the desorption energy of Gd from the hollow tungsten site by placing the Gd atom 5 Å away from the surface and applying the equation [31]:…”

A DFT study of O2 and Cl2 adsorption onto Al12N12 fullerene‐like nanocluster

“…Moreover, since the early 1980s, Cl 2 interaction onto different surfaces has enthralled many experimental and theoretical works . There are different articles in literature focusing on the adsorption property of Cl 2 , including semiconductors and metals . Recently, Pavlova et al applied DFT method for investigation of the interaction of Cl 2 on the (111) plane of copper.…”

“…[5][6][7][8] There are different articles in literature focusing on the adsorption property of Cl 2 , including semiconductors [5][6][7] and metals. [8][9][10][11] Recently, Pavlova et al [10] applied DFT method for investigation of the interaction of Cl 2 on the (111) plane of copper. Mitsutake et al [11] pointed to the dissociative adsorption of Cl 2 molecules onto the Al(001) surface using the local density functional approach and the ab initio norm-conserving pseudopotential method.…”