Infrared spectra of SF6(-) x HCOOH x Ar(n) (n = 0-2): infrared triggered reaction and Ar-induced reactive inhibition.
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.
JILA, NIST, and Department of Chemistry and Biochemistry, University of Colorado at Boulder, Boulder, Colorado 80309, USA.
Holger
H
Schneider
Kaito
K
Takahashi
Rex T
RT
Skodje
J Mathias
JM
Weber