Energy partitioning of the self-consistent field interaction energy of ScCO

Abstract

The SCF interaction energy for ScCO was partitioned into the electrostatic, polarization, exchange, and charge-transfer terms via the Morokuma analysis. This definition of polarization does not satisfy the Pauli exclusion principle and therefore, there is nothing to prevent the valence electrons of one fragment from collapsing into the core orbitals of the other fragment. To correct this problem, the polarization and charge-transfer terms were calculated in the presence of exchange. The dominant interactions were exchange repulsion, electrostatic attraction, and distortion of the wave function by polarization and charge transfer. Pi backbonding was the dominant distortion for the 4 Σ− 4s1 3dπ2 state, while sigma distortions dominated the 4s2 3d 1 states.