Negative ion-molecule reactions in sulfuryl halides

Infrared Spectra of the SO2F2– Anion in Solid Argon and Neon

“…For the SO 2 F x − family, SO 2 F − is the anion that has been the subject of a number of spectroscopic, crystallographic, ab initio, and density functional theory (DFT) studies, and it possesses a pyramidal geometry with the S−F bond length being 0.3 Å longer than the S−O bond length. 7−10 SO 2 F 3 − was observed as the reaction product of SO 2 F 2 and fluorine anions, 6 and its trigonal-bipyramidal geometry was confirmed by matrixisolation infrared spectroscopy and theoretical calculations. 8,11,12 Our knowledge on the SO 2 F 2 − anion has mainly been obtained from computational studies, 8 while experimental information regarding its structure and bonding is still unavailable, presumably because of the difficulties in the formation and stabilization of molecular anions.…”

“…Sulfur oxyfluorides are observed as the decomposition and hydrolysis products of SF 6 upon reactions with O 2 and H 2 O in plasma environments where SF 6 is used as the plasma etching gas and electron scavenger. − In addition to the neutral sulfur oxyfluorides such as SOF 2 , SOF 4 , and SO 2 F 2 , anionic species containing sulfur, oxygen, and fluorine are also present in the plasma. The reactivities of these anions have been the focus of a series of investigations that have helped in understanding their formation pathways as well as their thermochemical properties in the gas phase. − Since the reactivity is correlated with the geometry of the reactant, it is also necessary to identify the molecular structure of these anions. For the SO 2 F x – family, SO 2 F – is the anion that has been the subject of a number of spectroscopic, crystallographic, ab initio, and density functional theory (DFT) studies, and it possesses a pyramidal geometry with the S–F bond length being 0.3 Å longer than the S–O bond length. − SO 2 F 3 – was observed as the reaction product of SO 2 F 2 and fluorine anions, and its trigonal-bipyramidal geometry was confirmed by matrix-isolation infrared spectroscopy and theoretical calculations. ,, Our knowledge on the SO 2 F 2 – anion has mainly been obtained from computational studies, while experimental information regarding its structure and bonding is still unavailable, presumably because of the difficulties in the formation and stabilization of molecular anions …”

Electron collision with sulfuryl chloride (SO2Cl2) molecule

“…At energies beyond 2 eV the measured TCS starts to increase again. Between 3 and 6 eV, experiments on dissociative electron attachment [5,7,8] reveal formation of numerous negative fragment ions (e.g. Cl − , Cl − 2 , SO − 2 ), with the intensities peaked at about 5.1, 4.4 and 5.2 eV, respectively.…”

“…Studies on the electron-assisted processes involving SO 2 Cl 2 molecules started some decades ago; however, the respective data still remain scarce and fragmentary. To date, experimental works on e − -SO 2 Cl 2 reactions concerned just the formation of negative ions [5][6][7][8] and/or ionization [6] induced by the electron impact, but derived electron-scattering intensities were reported in arbitrary units only.…”

Electron attachment to sulfur oxyhalides: SOF2, SOCl2, SO2F2, SO2Cl2, and SO2FCl attachment rate coefficients, 300–900 K

“…There exist early electron beam studies in which anion products were identified following electron bombardment. [9][10][11][12] Wang and Lee 13 have measured electron attachment rate coefficients for SO 2 Cl 2 in a drift tube apparatus at room temperature, and Datskos and Christophorou 14 reported rate coefficients for SO 2 F 2 from 300 to 700 K, also with a drift tube apparatus. Attachment to SO 2 F 2 has also been studied in a high-temperature plasma jet and found to be a poor attacher at 2000 K. 15 SO 2 F 2 , widely used as a fumigant, has received attention of late because of the increase in the concentration of SO 2 F 2 in the atmosphere and its high global warming potential.…”