Thermodynamic stability in transition metal-containing dicationic diatomics: Examining the case of CrO2+

Author(s)

dos Santos, Levi Goncalves ; Franzreb, Klaus ; Ornellas, Fernando R.

• Document type: Journal article
• Source: Chemical Physics Letters; v. 771, p. 5-pg., 2021-03-31.

Abstract

High-level ab initio calculations -state-averaged CASSCF/MRCI/aug-cc-pV5Z) -were carried out to construct potential energy curves for a manifold of electronic states of the dication CrO2+ covering regions from equilibrium to the dissociation limit, thus quantifying the energetics involved. The ground state (X (3)Sigma(-)), correlating diabatically to the channel Cr2++ O avoids a crossing at similar to 10 a(0) and dissociates into a channel located 21.47 kcal/mol above the molecular ground state zero-point energy, thus establishing the thermodynamic stability of CrO2+, a fact not a priori expected. Spectroscopic parameters and an analysis of the triple bond character in this species are reported. (AU)

• FAPESP's process: 18/06591-4 - Spectroscopic studies of neutral and ionic diatomic systems and of molecular reactions of dications with molecules and atoms in the gas phase
• Grantee: Fernando Rei Ornellas
• Support Opportunities: Regular Research Grants