Conical intersections and nonadiabatic coupling terms in 1,3,5-C6H3F3+: A six state beyond Born-Oppenheimer treatment.

In order to circumvent numerical inaccuracy originating from the singularity of nonadiabatic coupling terms (NACTs), we need to perform kinetically coupled adiabatic to potentially coupled diabatic transformation of the nuclear Schrödinger Equation. Such a transformation is difficult to achieve for higher dimensional sub-Hilbert spaces due to inherent complicacy of adiabatic to diabatic transformation (ADT) equations. Nevertheless, detailed expressions of ADT equations are formulated for six coupled electronic states for the first time and their validity is extensively examined for a well-known radical cation, namely, 1,3,5- C 6 H 3 F 3 + (TFBZ+). While implementing this formulation, we compute ab initio adiabatic potential energy surfaces (PESs) and NACTs within the low-lying six electronic states ( X ̃ 2 E ′ ′ , Ã 2 A 2 ′ ′ , B ̃ 2 E ′ , and C ̃ 2 A 2 ′ ), where several types of nonadiabatic interactions, like Jahn-Teller conical intersections (CI), accidental CIs, accidental seams (series of degenerate points), and pseudo Jahn-Teller interactions can be observed over the Franck-Condon region of nuclear configuration space. Those interactions are depicted by exploring degenerate components of C–C asymmetric stretching, C–C symmetric stretching, and C–C–C scissoring motion (Q9x, Q9y, Q10x, Q10y, Q12x, and Q12y) to compute complete active space self-consistent field level adiabatic PESs and NACTs as implemented in the MOLPRO quantum chemistry package. Subsequently, we perform the ADT using our newly devised fifteen (15) ADT equations to locate the position of CIs, verify the quantization of NACTs, and to construct highly accurate diabatic PESs. [ABSTRACT FROM AUTHOR]