PCCP RSCPublishing ARTICLE This journal is © The Royal Society of Chemistry 2013 J. Name ., 2013, 00, 1-3 | 1 Cite this: DOI: 10.1039/x0xx00000x Received 00th January 2012, Accepted 00th January 2012 DOI: 10.1039/x0xx00000x www.rsc.org/ Modification of catalytic properties of the Au 4 nanocluster for the conversion of methane-to- methanol: Synergic effects of metallic adatoms and defective graphene support J. Sirijaraensre a,b and J. Limtrakul a,b,c,* Table S1. ZPE-corrected relative energies of the system along the steps of the catalytic cycle for the partial oxidation of methane by N 2 O over the graphene- deposited Au 5 catalyst. The energy of the isolated subsystems in their lowest-energy spin state is taken as zero. Relative Energy (kcal·mol -1 ) Steps Doublet spin-state Quartet spin-state Isolated systems 0.0 18.8 N 2 O adsorption -4.5 14.1 N 2 O decomposition transition state (TS1) 11.6 21.7 N 2 adsorption on Au 5 O -9.2 -2.1 N 2 desorption -5.9 1.4 CH 4 adsorption -9.4 2.0 C-H bond activation transition state (TS2) 5.9 16.8 Intermediate of C-H bond activation -32.8 -25.0 Two-centered recombination C-O formation transition state (TS3) 7.2 10.6 One-centered recombination CH 3 Shift transition state (TS3 B1 ) -17.3 -10.1 IV B intermediate -20.1 -34.5 C-O formation transition state (TS3 B2 ) 5.9 18.5 CH 3 OH adsorption -39.4 -20.6 CH 3 OH desorption -28.9 -10.1 Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics. This journal is © the Owner Societies 2015