In this work, based on first principles density functional theory, we have investigated the interaction of SO
3 molecule on three different substrates; (i) clean Al
2O
3 surface (0001) (ii) an isolated Ag
6 cluster and (iii) Ag
6 clusters deposited on the Al
2O
3 surface. All calculations were carried out using the plane wave based pseudopotential method under the framework of density functional theory. For the clean Al
2O
3 surface, the SO
3 molecule was adsorbed in parallel orientation on the surface resulting in an elongation of the S–O bond from 1.44 to 1.52 Å with interaction energy of 1.67 eV. In contrast, the interaction of SO
3 with Ag
6 was found to be weak with 0.4 eV interaction energy and 1.47 Å as the largest S–O bond length. Remarkably, when SO
3 molecule interacted with Ag
6 cluster deposited on the Al
2O
3 support, the binding was found to be higher than both Al
2O
3 and Ag
6 clusters in their isolated state. In particular, upon adsorption of SO
3 on Ag
6/@Al
2O
3, the S–O bond length was found to increases from 1.44 to 1.64 Å and the interaction energy was estimated to be 2.00 eV. As the bond elongation bears the signature of bond weakening, a comparison of the above three results clearly suggests that the dissociation barrier of S–O bond on the Ag
6@Al
2O
3 support will be significantly lower than that on the isolated Ag
6 or Al
2O
3 surface. The nature of chemical interaction of SO
3 on these three systems has been discussed based on the electronic density of states analysis.
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