Infrared spectra of SF6−⋅HCOOH⋅Arn (n=–2): Infrared triggered reaction and Ar-induced reactive inhibition

Abstract

We present the infrared spectra of SF(6)(-) x HCOOH x Ar(m) (m=0-2) complexes. We find that the binding motif involves a single hydrogen bond between the SF(6)(-) anion and the OH group of the formic acid, with the CH group weakly tethered to a neighboring F atom. Similar to the case of hydrated SF(6)(-), the SF bond involved in the (OH-F) bond is significantly stretched and weakened by the attachment of the HCOOH ligand. The bare complex undergoes reaction upon infrared absorption in the CH/OH stretching region of the formic acid moiety, leading predominantly to the formation of SF(4)(-) + 2HF + CO(2). The reaction can be inhibited by attachment of two Ar atoms. We discuss a likely reaction mechanism in the framework of ab initio calculations, suggesting that reaction proceeds via tunneling through the potential barrier.