Details

Autor(en) / Beteiligte

• Bie, Lihua
• Liu, Fang
• Li, Yanwei
• Dong, Tiange
• Gao, Jun
• Du, Likai
• Yuan, Qiaoxia

Titel

Spin crossover dynamics studies on the thermally activated molecular oxygen binding mechanism on a model copper complexElectronic supplementary information (ESI) available: The electronic structure results at different theoretical methods, the optimized geometry of monocopper model complexes, and further details of the dynamic trajectories. See DOI: 10.1039/c8cp02482k

Erscheinungsjahr

2018-06

Link zum Volltext

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• The theoretical description of the primary dioxygen (O 2 ) binding and activation step in many copper or iron enzymes, suffers from the intrinsically electronic non-adiabaticity of the spin flip events of the triplet dioxygen molecule ( 3 O 2 ), mediated by spin-orbit couplings. In this work, we presented the early-stage ultrafast spin flip dynamics of O 2 binding for a simplified monocopper complex, involving the coupled singlet and triplet electronic states. The on-the-fly trajectory surface hopping (TSH) simulations have identified the dynamical effects that may influence the mode of O 2 coordination (end-on vs. side-on), and the electronic structures can be viewed as complexes of molecular O 2 with Cu( i ) or as Cu( ii )-superoxide compounds. In addition, significant spin flip events are obversed within the sub-picosecond regime. We hope this work may provide complimentary insights on the traditional interpretation of O 2 binding on copper complexes and subsequent catalytic reaction mechanisms. The theoretical description of the primary dioxygen (O 2 ) binding and activation step in many copper or iron enzymes, suffers from the instrinsically electronic non-adiabaticity of the spin flip events of the triplet dioxygen molecule ( 3 O 2 ), mediated by spin-orbit couplings.