Adsorption and dissociation of the methanethiol (CH3SH) molecule on the Fe(100) surface.

These contributions explore interaction modes between the methanethoil (CH3SH) molecule and the Fe(100) surface via implementing accurate density functional theory (DFT) calculations with the inclusion of van der Waals corrections. We consider three adsorption sites over the Fe(100) surface, namely, top(T), bridge (B), and hollow (H) sites as potential catalytic active sites for the molecular and dissociative adsorption of the CH3SH molecule. The molecular adsorption structures are found to occupy either B or T sites with former sites holding higher stability by 0.17 eV. The inclusion of van der Waals corrections refound to slightly alter adsorption energies. For instance, adsorption energies increased by ~0.18 and ~0.21 eV for B and T structure, respectively, in reference to values obtained by the plain generalized gradient approximation (GGA) functional. A stability ordering of the dissociation products was found to follow the sequence (CH4, S) > (CH3, S, H) > (─SCH3, H) > (─CH3, SH). The differential charge density distributions were examined to underpin prominent electronic contributing factors. Direct fission of C─S bond in the CH3SH molecule attains exothermic values in the range 2.0 to 2.1 eV. The most energetically favorable sites for the surface‐mediated fission of the thiol's S─H bond correspond to the structure where the ─SCH3 and H are both situated on hollow sites with an adsorption energy of −2.43 eV. Overall, we found that inclusion of van der Waals functional to change the binding energies more noticeably in case of dissociative adsorption structures. The results presented herein should be instrumental in efforts that aim to design stand‐alone Fe desulfurization catalysts. [ABSTRACT FROM AUTHOR]