Electron attachment to microhydrated 4-nitro- and 4-bromo-thiophenol

0545409 - ÚFCH JH 2022 RIV GB eng J - Journal Article
Sala, Leo Albert - Sedmidubská, Barbora - Vinklárek, Ivo S. - Fárník, Michal - Schuermann, R. - Bald, I. - Med, J. - Slavíček, P. - Kočišek, Jaroslav
Electron attachment to microhydrated 4-nitro- and 4-bromo-thiophenol.
Physical Chemistry Chemical Physics. Roč. 23, č. 33 (2021), s. 18173-18181. ISSN 1463-9076. E-ISSN 1463-9084
R&D Projects: GA ČR(CZ) GA19-01159S; GA ČR(CZ) GX21-26601X
Institutional support: RVO:61388955
Keywords : temperature-dependence * detachment * anion * fragmentation * environment * competition * clusters * affinity * uracil * ion
OECD category: Physical chemistry
Impact factor: 3.945, year: 2021
Method of publishing: Limited access

We investigate the effect of microhydration on electron attachment to thiophenols with halogen (Br) and nitro (NO2) functional groups in the para position. We focus on the formation of anions upon the attachment of low-energy electrons with energies below 8 eV to heterogeneous clusters of the thiophenols with water. For nitro-thiophenol (NTP), the primary reaction channel observed is the associative electron attachment, irrespective of the microhydration. On the other hand, bromothiophenol (BTP) fragments significantly upon the electron attachment, producing Br- and (BTP-H)(-) anions. Microhydration suppresses fragmentation of both molecules, however in bromothiophenol, the Br- channel remains intense and Br(H2O)(n)(-) hydrated fragment clusters are observed. The results are supported by the reaction energetics obtained from ab initio calculations. Different dissociation dynamics of NTP and BTP can be related to different products of their plasmon induced reactions on Au nanoparticles. Computational modeling of the simplified BTP(H2O) system indicates that the electron attachment products reflect the structure of neutral precursor clusters the anion dissociation dynamics is controlled by the hydration site.
Permanent Link: http://hdl.handle.net/11104/0322103