Infrared spectra of SF6−⋅HCOOH⋅Arn (n = 0–2): Infrared triggered reaction and Ar-induced reactive inhibition

Schneider, Holger; Takahashi, Kaito; Skodje, Rex T.; Weber, J. Mathias

doi:doi:10.1063/1.3125960

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Full-dimensional ab initio potential energy surface and vibrational configuration interaction calculations for vinyl

The potential energy landscape and two permutationally invariant, full-dimensional ab initio-based potential energy surfaces (PESs) for the doublet vinyl radical, C2H3, are described. The first of the two surfaces, denoted as PES/S, describes the equivalent CH2CH global minimum and the saddle point separating them, planar and nonplanar H-atom migration saddle points, a methylcarbyne local minimum that is due to a Jahn–Teller conical intersection, and the saddle point connecting it with the glob...

Doppler widths in electron quasielastic scattering from molecular gases

Recent quasielastic electron scattering experiments on some molecular gases at Ee ≥ 1.8 keV have shown that the scattering is from single isotopes of the atomic components of the gas. The scattered electron lines at definite angles are Doppler broadened by the instantaneous kinetic energy (KE) of the scattering atoms. We calculated the KE of the scattering atoms by accounting for translation, rotation, and all normal modes of vibrations of the molecule. The results reveal some large and fundame...

We present the infrared spectra of SF₆⁻⋅HCOOH⋅Ar_m (m = 0–2) complexes. We find that the binding motif involves a single hydrogen bond between the SF₆⁻ 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 SF₆⁻, 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 SF₄⁻+2HF+CO₂. 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.

Article Outline

INTRODUCTION
EXPERIMENTAL SETUP
CALCULATIONS
RESULTS AND DISCUSSION
1. Structure and vibrational assignments
2. Infrared triggered reactions
SUMMARY AND CONCLUSIONS

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KEYWORDS and PACS

Keywords

argon compounds, hydrogen bonds, infrared spectra, organic compounds, reaction kinetics theory, solvation, spectrochemical analysis, sulphur compounds, tunnelling

PACS

82.80.Dx

Analytical methods involving electronic spectroscopy
82.20.Db

Transition state theory and statistical theories of rate constants
82.30.Nr

Association, addition, insertion, cluster formation
78.30.Jw

Organic compounds, polymers

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http://dx.doi.org/10.1063/1.3125960

PUBLICATION DATA

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0021-9606 (print)

1089-7690 (online)

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American Institute of Physics

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