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We demonstrate for the first time that when a methanethiol adsorbed on theregular Cu(111) surface, the dissociative structure is thermodynamically morestable than the intact one. The computational results show that at lowtemperature the methanethiol adsorbate prefers the atop site of the regularCu(111) surface. As the temperature is increased, the S-H bond is broken andthe methylthiolate favors the hollow sites. On the defected Cu(111) surface,the dissociative configuration is still thermodynamically more stable than thenondissociative one. The calculation indicates that the hydrogen initiallyattached to the sulfur would like to form a bond with the copper surface ratherthan desorb from it. Even though both copper and gold are the noble metal, thestability of the methanethiol adsorption on the Cu(111) substrate is almost thereverse of that on the Au(111).

The CH3SH molecule deposited on Cu(111) and deprotonation