This theoretical work constructs beyond born-oppenheimer diabatic surfaces and computes photoelectron and mass-analyzed threshold ionization spectra, indicating nonadiabatic coupling.
Theoretically “exact” and numerically “accurate” Beyond Born–Oppenheimer (BBO)‐based diabatic Hamiltonian for an aromatic radical cation, namely, o‐HF, is constructed theoretically for the first time, where the low‐lying five electronic states (, , , , and ) are nonadiabatically coupled with each other, exhibiting conical intersections (CIs)/seams due to accidental Jahn–Teller (JT) couplings as well as depicting pseudo‐Jahn–Teller interactions. Once the diabatic PESs and couplings are constructed, those are used to execute multistate multimode nuclear dynamics for generating photoelectron (PE) and mass‐analyzed threshold ionization spectra of the neutral analog. The calculated PE spectra for , , , and states originated from the BBO‐based diabatic Hamiltonian in conjunction with time‐dependent discrete variable representation (TDDVR) dynamics show peak‐by‐peak correspondence with the experimental spectral bands as well as with other theoretical findings.
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Hazra et al. (2025) studied this question.
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