10.1021/acs.jpca.5b04737.s001 Chen-Chi Lee Chen-Chi Lee Hsin-Tsung Chen Hsin-Tsung Chen Adsorption and Reaction of C<sub>2</sub>H<sub>4</sub> and O<sub>2</sub> on a Nanosized Gold Cluster: A Computational Study American Chemical Society 2015 reaction mechanisms 38 nanoparticle LH C 2H Nanosized Gold Cluster eV calculation results show NEB DFT O 2 LDOS ethylene adsorption 2015-08-06 00:00:00 Journal contribution https://acs.figshare.com/articles/journal_contribution/Adsorption_and_Reaction_of_C_sub_2_sub_H_sub_4_sub_and_O_sub_2_sub_on_a_Nanosized_Gold_Cluster_A_Computational_Study/2143504 We have investigated the adsorption and reaction mechanisms of C<sub>2</sub>H<sub>4</sub> and O<sub>2</sub> catalyzed by a Au<sub>38</sub> nanoparticle based on periodic density-functional theory (DFT) calculations. The configurations of the adsorption of C<sub>2</sub>H<sub>4</sub>/Au<sub>38</sub>, O<sub>2</sub>/Au<sub>38</sub>, and O/Au<sub>38</sub> as well as the coadsorption of C<sub>2</sub>H<sub>4</sub>–O<sub>2</sub>/Au<sub>38</sub> were predicted. The calculation results show that C<sub>2</sub>H<sub>4</sub>, O<sub>2</sub>, and O are preferably bound at top (T), bridge (B), and hexagonal (h) sites with adsorption energies of −0.66, −0.99, and −3.93 eV, respectively. The detailed reaction mechanisms for ethylene epoxidation on the Au<sub>38</sub> nanoparticle has been illustrated using the nudged elastic band (NEB) method. The oxidation process takes place via the Langmuir–Hinshelwood (LH) mechanism to generate ethylene oxide and acetaldehyde. The overall reaction of C<sub>2</sub>H<sub>4</sub> + O<sub>2</sub> + Au<sub>38</sub> → ethylene oxide + O/Au<sub>38</sub> is exothermic by 2.20–2.40 eV whereas those are 3.03–3.08 eV for the production of acetaldehyde and O/Au<sub>38</sub>. The nature of the interaction between the adsorbate and gold nanocluster has been analyzed by the detailed electronic local density of states (LDOS) to understand the high catalytic activity of the gold nanoclusters.