A re-examination of the infrared and ultraviolet spectroscopy of trifluoroacetyl fluoride and trifluoroacetyl chloride: An experimental and theoretical study

J. S. Francisco; I. H. Williams

doi:10.1016/0584-8539(92)80121-C

A re-examination of the infrared and ultraviolet spectroscopy of trifluoroacetyl fluoride and trifluoroacetyl chloride: An experimental and theoretical study

J. S. Francisco, I. H. Williams

Department of Chemistry

Wayne State University

Research output: Contribution to journal › Article › peer-review

Abstract

The fundamental IR vibrational modes of trifluoroacetyl fluoride CF₃C(O)F and trifluoroacetyl chloride CF₃C(O)Cl have been re-examined by ab initio molecular orbital calculations and compared with literature assignments. Several bands of the IR spectrum are reassigned. The Q-branch and integrated absorption cross-sections have been measured for ν₁, ν₃, ν₄ and ν₁₁ fundamental bands for both pressurized and unpressurized samples on each molecule. The UV absorption spectra of CF₃C(O)F and CF₃C(O)Cl show a structureless continuum with a maximum at 21Onm (σ_max=3.20±0.02 × 10^-20 cm² molecule^-1) and 255 nm (σ_max=7.66±0.26 × 10^-20 cm² molecule^-1), respectively. The nature of the electronic transition giving rise to the UV absorption spectrum for CF₃C(O)F and CF₃C(O)Cl has been examined by ab initio molecular orbital calculations. It is attributed to the A¹A″←X¹A′ electronic transition.

Original language	English
Pages (from-to)	1115-1126
Number of pages	12
Journal	Spectrochimica Acta Part A: Molecular Spectroscopy
Volume	48
Issue number	8
DOIs	https://doi.org/10.1016/0584-8539(92)80121-C
Publication status	Published - 1 Aug 1992

Funding

Acknowledgements--We are grateful to NATO for the award of a travel grant to J. S. Francisco and I. H. Williams and to the SERC for provision of CRAY computer time. J. S. Francisco thanks the Pittsburgh Computer Center for a generous allocation of computer time to complete this work. The A. P. Sloan Foundation is gratefully acknowledged for support of this work. We also thank G. Szulczewski for his assistance.

ASJC Scopus subject areas

General Engineering

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10.1016/0584-8539(92)80121-C

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title = "A re-examination of the infrared and ultraviolet spectroscopy of trifluoroacetyl fluoride and trifluoroacetyl chloride: An experimental and theoretical study",

abstract = "The fundamental IR vibrational modes of trifluoroacetyl fluoride CF3C(O)F and trifluoroacetyl chloride CF3C(O)Cl have been re-examined by ab initio molecular orbital calculations and compared with literature assignments. Several bands of the IR spectrum are reassigned. The Q-branch and integrated absorption cross-sections have been measured for ν1, ν3, ν4 and ν11 fundamental bands for both pressurized and unpressurized samples on each molecule. The UV absorption spectra of CF3C(O)F and CF3C(O)Cl show a structureless continuum with a maximum at 21Onm (σmax=3.20±0.02 × 10-20 cm2 molecule-1) and 255 nm (σmax=7.66±0.26 × 10-20 cm2 molecule-1), respectively. The nature of the electronic transition giving rise to the UV absorption spectrum for CF3C(O)F and CF3C(O)Cl has been examined by ab initio molecular orbital calculations. It is attributed to the A1A″←X1A′ electronic transition.",

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N2 - The fundamental IR vibrational modes of trifluoroacetyl fluoride CF3C(O)F and trifluoroacetyl chloride CF3C(O)Cl have been re-examined by ab initio molecular orbital calculations and compared with literature assignments. Several bands of the IR spectrum are reassigned. The Q-branch and integrated absorption cross-sections have been measured for ν1, ν3, ν4 and ν11 fundamental bands for both pressurized and unpressurized samples on each molecule. The UV absorption spectra of CF3C(O)F and CF3C(O)Cl show a structureless continuum with a maximum at 21Onm (σmax=3.20±0.02 × 10-20 cm2 molecule-1) and 255 nm (σmax=7.66±0.26 × 10-20 cm2 molecule-1), respectively. The nature of the electronic transition giving rise to the UV absorption spectrum for CF3C(O)F and CF3C(O)Cl has been examined by ab initio molecular orbital calculations. It is attributed to the A1A″←X1A′ electronic transition.

AB - The fundamental IR vibrational modes of trifluoroacetyl fluoride CF3C(O)F and trifluoroacetyl chloride CF3C(O)Cl have been re-examined by ab initio molecular orbital calculations and compared with literature assignments. Several bands of the IR spectrum are reassigned. The Q-branch and integrated absorption cross-sections have been measured for ν1, ν3, ν4 and ν11 fundamental bands for both pressurized and unpressurized samples on each molecule. The UV absorption spectra of CF3C(O)F and CF3C(O)Cl show a structureless continuum with a maximum at 21Onm (σmax=3.20±0.02 × 10-20 cm2 molecule-1) and 255 nm (σmax=7.66±0.26 × 10-20 cm2 molecule-1), respectively. The nature of the electronic transition giving rise to the UV absorption spectrum for CF3C(O)F and CF3C(O)Cl has been examined by ab initio molecular orbital calculations. It is attributed to the A1A″←X1A′ electronic transition.

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A re-examination of the infrared and ultraviolet spectroscopy of trifluoroacetyl fluoride and trifluoroacetyl chloride: An experimental and theoretical study

Abstract

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