Reaction of CO2 with Atomic Transition Metal M+/0/- Ions: A Theoretical Study

Yunhai Sun; Xiaoli Sun; Xuri Huang

doi:10.1021/acs.jpca.8b01917

Reaction of CO₂ with Atomic Transition Metal M^+/0/- Ions: A Theoretical Study

J Phys Chem A. 2018 Jul 12;122(27):5848-5860. doi: 10.1021/acs.jpca.8b01917. Epub 2018 Jun 27.

Authors

Yunhai Sun¹, Xiaoli Sun¹, Xuri Huang¹

Affiliation

¹ Institute of Theoretical Chemistry , Jilin University , Changchun 130023 , People's Republic of China.

PMID: 29897778
DOI: 10.1021/acs.jpca.8b01917

Abstract

The activation of carbon dioxide mediated by the first row 3d transition metal (TM) M^+/0/- atomic ions was studied theoretically. Theoretical calculations show left-hand transition-metal ions Sc⁺, Sc, Ti⁺, Ti, and V can mediate oxygen atom transfer (OAT) from carbon dioxide. In the anionic system, for early transition metal ions (Sc to Cr), [OM-CO]^- are more stable than [M-OCO]^-, while the others favor binding formation, [M-OCO]^-. TSR was observed in O atom transfer. The OAT reaction is exothermic only for the first three transition metal cations and atoms (Sc^+/0, Ti^+/0, and V^+/0), Fe⁰ and all the anions except Cu^- and Zn^-. Furthermore, in most case, reaction enthalpy, and energy barrier of OAT for the cationic system is the highest, and the anionic system is the lowest. We discuss the performances of 18 methods on the energies and structures.