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arxiv 2505.00532 v1 pith:G7ISYTHM submitted 2025-05-01 physics.atm-clus physics.chem-phquant-ph

Observation of Resonant Tunneling from Molecular Shape into Vibronic Feshbach Resonances Followed by Mode-Specific Fragmentation

classification physics.atm-clus physics.chem-phquant-ph
keywords dissociationelectronenergyresonancesresonantshapevibrationalvibronic
verification ladder T0 review T1 audit T2 compute T3 formal T4 reserved
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We present a kinematically complete study of dissociative electron attachment (DEA) in linear OCS molecules, focusing on how electrons resonantly attach and trigger dissociation. Near the Franck-Condon regime, DEA is dominated by molecular shape resonances, where transient OCS$^-$ states form with high vibrational amplitudes, spectroscopically evident as broad features in DEA cross-sections. As the electron beam energy increases from 5.5 to 6.0 eV, S$^-$ population shifts from lower to higher-energy highly dense bending vibrational states, reinforcing our findings on dipole-forbidden vibronic intensity borrowing. Our advanced potential energy curve calculations, employing the Equation-of-motion coupled cluster singles and doubles for electron attachment (EA-EOMCCSD) method, reveal that beyond the shape resonance, non-adiabatic resonant tunneling governs the avoided crossings, dynamically generating three mode-specific vibronic Feshbach resonances before complete dissociation into three distinct kinetic energy bands of S$^-$. Our theoretical results probe most of the experimental observations quantitatively and qualitatively. These insights deepen our fundamental understanding of resonance-mediated dissociation in electron-molecule resonant scattering, with broader implications for quantum mechanics, plasma physics, vibrational revival, astrochemistry, and radiation damage research.

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