N2O2, N2O2− and N2O22−: structures, energetics and NN bonding

Density Functional Theory Molecular Cluster Study of Copper Interaction with Nitric Oxide Dimer in Cu−ZSM-5 Catalysts

“…32 The B3LYP/6-31G* calculations in this work give E a ) -1.3 eV and confirm the experimental data on the formation of surface anion π-radical (N 2 O 2 ) -on electron donor sites of supported organo-zirconium surface complex. 33 We used the molecular cluster (HO) 3 Al-O2-Cu2-O1-Cu1 ( Figure 1a) to model the CAS in Cu-ZSM-5 zeolites and to study its interaction with ONNO.…”

“…31 The observation of the IVT bands in UV-vis spectra of Cu-ZSM-5 definitely indicates that the Cu(I)/Cu(II) recharging potential is low for copper oxide chain structures in which stabilization of the "pair" copper state Cu(II)-e --Cu(II) is possible. Together with high electron affinity of the molecular dimer ONNO (E a ) -1.3 ÷ -1.7 eV), 32 this may result in the formation of surface anion π-radical (ONNO) -in such systems that is similar to the organo-zirconium surface complex with (N 2 O 2 ) -observed by ESR. 33 On the other hand, the formation of a strong bond between nitrogen atoms in such radical (N-N ) 1.4 Å) 32 clearly indicates that decomposition of the intermediate form -(N 2 O 2 ) -to a N 2 O molecule and -(O) -is the preferred decomposition pathway.…”

“…Together with high electron affinity of the molecular dimer ONNO (E a ) -1.3 ÷ -1.7 eV), 32 this may result in the formation of surface anion π-radical (ONNO) -in such systems that is similar to the organo-zirconium surface complex with (N 2 O 2 ) -observed by ESR. 33 On the other hand, the formation of a strong bond between nitrogen atoms in such radical (N-N ) 1.4 Å) 32 clearly indicates that decomposition of the intermediate form -(N 2 O 2 ) -to a N 2 O molecule and -(O) -is the preferred decomposition pathway. Indeed, the ONNO dimer adsorbed on the metal surface Ag-(111) shows a surprising low-temperature reactivity producing directly N 2 O adsorbed molecules with a low activation energy of 2.0 kcal/mol: (ONNO) ad w N 2 O ad + O ad .…”

Communication: Towards catalytic nitric oxide reduction via oligomerization on boron doped graphene

“…Indeed, in a series of combined experimental and theoretical studies we have explored the electron catalyzed oligomerisation and decomposition of (NO) − n , n = 2-8. 15,18,19 Here, we combine our insights of NO chemistry and Lewis acid-base socket-plug functionality of boron doped graphene towards an incoming nucleophile to explore the possible catalytic properties of the latter towards direct disproportionation of NO to N 2 + O 2 . Thus, our study is complementary to recent NO reduction studies which utilize edge states of graphene and employ graphene as reducing agent in producing, e.g., CO 2 .…”

Critical comparison of single-reference and multireference coupled-cluster methods: Geometry, harmonic frequencies, and excitation energies of N2O2

“…So far in the literature 8,13,14,16,17,[22][23][24] only the CASPT2 result 23 shows both geometries and vibrational frequencies in fair agreement with experiment. However, it is hard to gauge the reliability of these results since the frequencies were obtained only with a 6-311G(d) basis set, and no systematic studies of convergence with respect to the active space and basis set size are available.…”