Electronic processes in NO dimerization on Ag and Cu clusters: DFT and MRMP2 studies

Experimentally observed NO dimerization on Cu and Ag surfaces is surprising because binding energy of NO dimer is very small in gas phase. MRMP2, MP2 to MP4, CCSD(T), and DFT studies of NO dimerization on Ag₂ and Cu₂ clusters disclosed that the CCSD(T) method could be applied to this reaction on Ag₂ and Cu₂ unlike NO dimerization in gas phase which exhibits significantly large nondynamical electron correlation effect. Charge-transfer (CT) from Ag₂ and Cu₂ to NO moieties plays important role in N N bond formation between two NO molecules. This CT considerably decreases nondynamical correlation effect. Also, the DFT method could be applied to this NO dimerization, if appropriate DFT functional is used; all pure functionals examined here and most of the hybrid functionals underestimated the activation barrier (E_a), while only ωB97X provided E_a similar to CCSD(T)-calculated value. NO dimerization on similar Cu₂ and Cu₅ needs moderately larger E_a than those on Ag₂ and Ag₅, because frontier orbital participating in the CT exists at lower energy in Cu₂ and Cu₅ than in Ag₂ and Ag₅. The E_a decreases in the order Ag₂ >> Ag₃₈ > Ag₇ ∼ Ag₅ and the reaction energy (ΔE) is positive (endothermic) in Ag₂ but significantly negative in Ag₃₈, Ag₇, and Ag₅, indicating that various Ag clusters could be effective for NO dimerization except for Ag₂. The decreasing order of E_a and increasing order of exothermicity are attributed to increasing order of the frontier orbital energy of Ag₂ < Ag₃₈ < Ag₇ ∼ Ag₅. © 2018 Wiley Periodicals, Inc.