Infrared absorption spectra, radiative efficiencies, and global warming potentials of perfluorocarbons: Comparison between experiment and theory

被引:90
作者
Bravo, Ivan [1 ]
Aranda, Alfonso [1 ]
Hurley, Michael D. [2 ]
Marston, George [3 ]
Nutt, David R. [3 ]
Shine, Keith P. [4 ]
Smith, Kevin [5 ]
Wallington, Timothy J. [2 ]
机构
[1] Univ Castilla La Mancha, Dept Phys Chem, Fac Chem, E-13071 Ciudad Real, Spain
[2] Ford Motor Co, Syst Analyt & Environm Sci Dept, Dearborn, MI 48121 USA
[3] Univ Reading, Dept Chem, Reading RG6 6AD, Berks, England
[4] Univ Reading, Dept Meteorol, Reading RG6 6BB, Berks, England
[5] Rutherford Appleton Lab, Space Sci & Technol Dept, Didcot OX11 0QX, Oxon, England
基金
英国工程与自然科学研究理事会; 英国自然环境研究理事会;
关键词
VIBRATIONAL FREQUENCIES; CFC SUBSTITUTES; CROSS-SECTIONS; INTENSITIES; HALOCARBONS;
D O I
10.1029/2010JD014771
中图分类号
P4 [大气科学(气象学)];
学科分类号
0706 ; 070601 ;
摘要
Experimentally and theoretically determined infrared spectra are reported for a series of straight-chain perfluorocarbons: C2F6, C3F8, C4F10, C5F12, C6F14, and C8F18. Theoretical spectra were determined using both density functional (DFT) and ab initio methods. Radiative efficiencies (REs) were determined using the method of Pinnock et al. (1995) and combined with atmospheric lifetimes from the literature to determine global warming potentials (GWPs). Theoretically determined absorption cross sections were within 10% of experimentally determined values. Despite being much less computationally expensive, DFT calculations were generally found to perform better than ab initio methods. There is a strong wavenumber dependence of radiative forcing in the region of the fundamental C-F vibration, and small differences in wavelength between band positions determined by theory and experiment have a significant impact on the REs. We apply an empirical correction to the theoretical spectra and then test this correction on a number of branched chain and cyclic perfluoroalkanes. We then compute absorption cross sections, REs, and GWPs for an additional set of perfluoroalkenes.
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页数:12
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