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Article Abstract
This work investigates Jahn-Teller conical intersections (CoIns) and the pseudo-Jahn-Teller effect on the formations and transformations of the low-lying singlet metal-ligand charge transfer (MLCT) excited states during the ultrafast evolution process of photoexcited [Ru(tpy)] (tpy = 2,2':6',2″-terpyridine). Longuet-Higgins' geometric phase analyses indicate that the potential energy surface (PES) crossing between charge transfer states MLCT and MLCT is a CoIn, originating from the change in diabatic Hamiltonian matrix elements around the CoIn. Moreover, an ⊗( + ) Jahn-Teller distortion can occur around the Franck-Condon and minimal energy CoIn (MECI) configurations, causing the molecule to distort spontaneously from the high-symmetry configuration to symmetry configurations that are close to it. Furthermore, the pseudo-Jahn-Teller effect can cause the molecule to distort further from to geometries since the former is a second-order saddle point on the whole dimensional PES but the latter is a true minimum. Eight minima in total are symmetrically distributed around the MECI. These minima are connected by the interligand electron transfer, the charge transfer, and the butterfly-like conformational inversion reactions, all of which have extremely small energy barriers.
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