biostudies-literatureKumar SMinisterio de UniversidadesSpanish Ministerio de Ciencia e InnovaciónFundação para a Ciência e TecnologiaSpanish National Research Council4820https://www.ebi.ac.uk/biostudies/studies/S-EPMC9369944biostudies-literatureUnknown27(15)The geometrical effect of chlorine atom positions in polyatomic molecules after capturing a low-energy electron is shown to be a prevalent mechanism yielding Cl₂^-. In this work, we investigated hexachlorobenzene reduction in electron transfer experiments to determine the role of chlorine atom positions around the aromatic ring, and compared our results with those using <i>ortho</i>-, <i>meta</i>- and <i>para</i>-dichlorobenzene molecules. This was achieved by combining gas-phase experiments to determine the reaction threshold by means of mass spectrometry together with quantum chemical calculations. We also observed that Cl₂^- formation can only occur in 1,2-C₆H₄Cl₂, where the two closest C-Cl bonds are cleaved whiMolecules (Basel, Switzerland)Sensing the <i>ortho</i> Positions in C₆Cl₆ and C₆H₄Cl₂ from Cl₂^- Formation upon Molecular Reduction.PMC9369944PTDC/FIS-AQM/31281/2017PID2019-104727RBC21PID2019-104727RB-C21PD/BD/142846/2018PD/BD/142831/2018 and COVID/BD/152673/2022CEFITEC (UIDB/00068/2020)LINKA20085RaBBiT, PD/00193/2012UCIBIO (UIDB/04378/2020)Maihom TRomero JGarcia GProbst MLimao-Vieira PKumar SfalseSensing the <i>ortho</i> Positions in C₆Cl₆ and C₆H₄Cl₂ from Cl₂^- Formation upon Molecular Reduction.The geometrical effect of chlorine atom positions in polyatomic molecules after capturing a low-energy electron is shown to be a prevalent mechanism yielding Cl₂^-. In this work, we investigated hexachlorobenzene reduction in electron transfer experiments to determine the role of chlorine atom positions around the aromatic ring, and compared our results with those using <i>ortho</i>-, <i>meta</i>- and <i>para</i>-dichlorobenzene molecules. This was achieved by combining gas-phase experiments to determine the reaction threshold by means of mass spectrometry together with quantum chemical calculations. We also observed that Cl₂^- formation can only occur in 1,2-C₆H₄Cl₂, where the two closest C-Cl bonds are cleaved whi2022-01-01T00:00:00Z2022 Jul2025-04-05T08:55:44.771Z2025-02-19T03:32:08.311ZS-EPMC93699443595676910.3390/molecules27154820