Structure and bonding in first-row transition metal dicarbide cations MC2+

Area of Science:

• Quantum Chemistry
• Computational Materials Science
• Inorganic Chemistry

Background:

• Transition metal dicarbides are of interest due to their unique bonding and potential applications.
• Understanding the stability and properties of their cationic forms is crucial for experimental synthesis and characterization.

Purpose of the Study:

• To conduct a theoretical investigation of first-row transition metal dicarbide cations (MC2+).
• To predict molecular properties that can aid in the experimental detection of these species.
• To analyze the structural preferences and bonding characteristics of MC2+ compounds.

Main Methods:

• Density Functional Theory (DFT) calculations were employed.
• Topological analysis of electronic density was performed.
• Valence orbital interactions were analyzed to understand bonding.

Main Results:

• Most MC2+ compounds exhibit a preference for a C2v symmetric arrangement over a linear geometry.
• The C2v isomer is particularly favored for early transition metals.
• Copper dicarbide cation (CuC2+) is predicted to have its global minimum in the linear isomer.
• Isomerization barriers between cyclic and linear species are generally low.
• C2v isomers typically adopt T-shaped structures.
• Early transition metal MC2+ compounds show higher dissociation energies compared to late transition metal analogues.
• Dissociation energies for MC2+ are generally lower than their neutral counterparts.

Conclusions:

• The study provides insights into the structural preferences and stability of first-row transition metal dicarbide cations.
• Predicted properties can guide experimental efforts in synthesizing and detecting these novel species.
• The bonding in MC2+ is interpretable through valence orbital interactions.