Observation of Renner–Teller and predissociation coupled vibronic intensity borrowing in dissociative electron attachment to OCS

Abstract

We use a time-of-flight-based velocity map imaging method to look into the dissociative electron attachment to a linear OCS molecule at electron beam energies ranging from 4.5 to 8.5 eV. The conical time-gated wedge slice imaging method is utilized to extract fragments’ slice images, kinetic energy (KE), and angular distributions, which provide a complete kinematic understanding of this experiment on the dissociative electron attachment process. We observe that the formation of S− is relatively higher than the O− product. Three distinct dissociative KE bands of S−/OCS have been observed for the 5.0 and 6.5 eV resonance positions. We notice a prominent rovibrationally coupled bimodality for each KE band in the variation of the most probable KE values. When the electron energy is changed from 5.5 to 6.0 eV, we observed vibronic intensity borrowing in the highest momentum band of S− via the Σ → Π symmetric dipole-forbidden transitions within the 1.5 eV energy gap. Multiple peaks in the angular distributions of S− and their modeling indicate the presence of Renner–Teller vibronic splitting. Using Q-Chem’s implemented complex absorbing potential-equation of motion-electron affinity coupled cluster singles and doubles aug-cc-pVDZ+4s3p level of multireference-based electronic structure theory, we confirm the presence of OCS temporary negative ion bending vibrations and Renner–Teller vibronic splittings for the Π symmetric states. Additionally, we notice the presence of a non-radiative predissociation continuum (bringing down the rotational spectrum) and speed-dependent angular anisotropy in the S− fragmentation. Our findings at the resonance of OCS at 6.5 eV closely align with the prediction of vibronic intensity borrowing by Orlandi and Siebrand [J. Chem. Phys. 58, 4513 (1973)].