0544169 - ÚOCHB 2022 RIV US eng J - Článek v odborném periodiku
Košťál, Vojtěch - Březina, Kryštof - Maršálek, O. - Jungwirth, Pavel
Benzene Radical Anion Microsolvated in Ammonia Clusters: Modeling the Transition from an Unbound Resonance to a Bound Species.
Journal of Physical Chemistry A. Roč. 125, č. 26 (2021), s. 5811-5818. ISSN 1089-5639. E-ISSN 1520-5215
Grant CEP: GA MŠMT(CZ) EF16_019/0000729
Institucionální podpora: RVO:61388963
Klíčová slova: fragment potential method * photoelectron-spectroscopy * spectra
Obor OECD: Physical chemistry
Impakt faktor: 2.944, rok: 2021
Způsob publikování: Omezený přístup
https://doi.org/10.1021/acs.jpca.1c04594

The benzene radical anion, well-known in organic chemistry as the first intermediate in the Birch reduction of benzene in liquid ammonia, exhibits intriguing properties from the point of view of quantum chemistry. Notably, it has the character of a metastable shape resonance in the gas phase, while measurements in solution find it to be experimentally detectable and stable. In this light, our previous calculations performed in bulk liquid ammonia explicitly reveal that solvation leads to stabilization. Here, we focus on the transition of the benzene radical anion from an unstable gas-phase ion to a fully solvated bound species by explicit ionization calculations of the radical anion solvated in molecular clusters of increasing size. The computational cost of the largest systems is mitigated by combining density functional theory with auxiliary methods including effective fragment potentials or approximating the bulk by polarizable continuum models. Using this methodology, we obtain the cluster size dependence of the vertical binding energy of the benzene radical anion converging to the value of −2.3 eV at a modest computational cost.
Trvalý link: http://hdl.handle.net/11104/0321219