High-Level ab InitioPredictions for the Ionization Energies, Bond Dissociation Energies, and Heats of Formation of Vanadium Methylidene, Vanadium Methyl Species, and Their Cations (VCH2/VCH2+, VCH3/VCH3+)

The ionization energies of VCH2and VCH3, the various 0 K bond dissociation energies (D0s) in their neutrals and cations, and their respective heats of formation at 0 and 298 K are computed by the single-reference, wave function-based CCSDTQ/CBS procedure. The core of the composite method is the approximation to the complete basis set (CBS) limit at the coupled cluster (CC) level which includes up to full quadruple excitations. The zero-point vibrational energy, core–valence correlation, spin–orbit coupling, and scalar relativistic effects have their contributions incorporated in an additive manner. For the species in the current study, this protocol requires geometry optimizations and harmonic frequency calculations practically no higher than the CCSD(T)/aug-cc-pwCVTZ and CCSD(T)/aug-cc-pVTZ levels, respectively. The present calculations successfully predict D0(V+–CH3) = 2.126 eV and D0(V+–CH2) = 3.298 eV in remarkable agreement with the data recently measured by a spin–orbit state selected V++ CH4collision experiment (Phys. Chem. Chem. Phys. 2021, 23, 273–286). The good accord encourages the use of CCSDTQ/CBS protocol in thermochemical predictions of various feasible product channels identified in methane activation by transition metal species.