preprints.org > chemistry and materials science > theoretical chemistry > doi: 10.20944/preprints202410.1939.v1

Preprint Article Version 1 This version is not peer-reviewed

Version 1 : Received: 23 October 2024 / Approved: 24 October 2024 / Online: 24 October 2024 (17:05:58 CEST)

The distortions and instability of high-symmetry configurations of polyatomic systems in nondegenerate states are usually ascribed to the pseudo-Jahn-Teller effect (PJTE). The geometries of hypericin, isohypericin, and fringelite D were optimized within various symmetry groups. Group-theoretical treatment and (TD-)DFT calculations were used to identify the corresponding electronic states during the symmetry descent. The symmetry descent paths (up to the stable structures without any imaginary vibrations) were determined using the corresponding imaginary vibrations as their kernel subgroups starting from the highest possible symmetry group. The vibronic interaction between the ground and excited electronic states relates to an increasing energy difference of both states during the symmetry decrease. This criterion was used to identify possible PJTE. We have shown that the PJTE in these naturally occurring compounds explains only the symmetry descent paths C2v → C2 and C2v → Cs in hypericin, and the D2h → C2v, D2h → C2v → Cs, and D2h → C2h ones in fringelite D. The electric dipole moments of hypericin and its analogs are determined prevailingly by the mutual orientations of the hydroxyl groups. The same holds for the energies of frontier orbitals in these systems, but their changes during the symmetry descent are less significant.

M06-2X hybrid functional; natural compounds; molecular symmetry; non-degenerate electronic states; excitation energy

Chemistry and Materials Science, Theoretical Chemistry

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