A theoretical investigation with high-level multireference methods is performed to reveal the Jahn-Teller origin of the triplet and singlet bent structures for CH2, CCl2, NH2+, and NCl2+ molecules and rationalize the relative energy ordering of the lowest singlet and triplet states. At the highest-symmetry linear configurations of these triatomic systems, the Pseudo Jahn-Teller effect (PJTE) between the ground state 3σg- and excited state 3Πu upon the bending mode, denoted as (3σg-+3Πu)⊗πu, is the reason of producing triplet 3B1 bent structures, and the combined PJTE of (1δg + 1Πu) ⊗ πu and Renner-Teller effect (RTE) of 1δg state result in the formations of singlet 1A1 and 1B1 minima. The PJTE of "δ-Π" plays a dominant role for the instability of degenerate Delta state which is subject to RTE. The spin-crossover induced by PJTE is responsible for the reversed order of singlet and triplet ground states in CH2/NH2+ and CCl2/NCl2+. The different singlet-triplet energy separations of those molecules can be rationalized from different Jahn-Teller vibronic coupling intensity at linear configurations. © 2014 Elsevier B.V.
Liu, Y. (2014). Singlet-triplet separation induced by the Pseudo Jahn-Teller effect examples: The CX2 and NX2+ (X=H, Cl) molecules. Computational and Theoretical Chemistry, 1044, 94–100. https://doi.org/10.1016/j.comptc.2014.06.013