DFT Study of Photochemical Properties and Radiative Forcing Efficiency Features of the Stereoisomers cis- and trans-CHCl═CH-CF3.

Abstract

The accurate assessment of radiative forcing efficiency (RFE) of a greenhouse gas is based on the precise knowledge of its structure and infrared absorption spectrum. The present work investigates the UV-vis absorption spectra and IR absorption spectra that are used for the determination of RFE of the short-lived compounds, cis- and trans-CHCl═CHCF3 (CTFP). These investigations were carried out with six different density functional theory (DFT) methods B3LYP, CAM-B3LYP, M06, M06-2X, TPSS0, and ωB97X-D associated to the basis set 6-31G(3df). Therefrom, the relative populations of the two states cis and trans for temperatures over the range 220-370 K at 1 atm and along the atmospheric altitude were assessed. It turns out that trans-CTFP is the abundant component between the two states. This review reveals that B3LYP and M06 reproduce well the experimental results of UV-vis spectra of trans-CTFP. As for cis-CTFP, EOM-CCSD is not well fitted by DFT methods. The cis- to trans-CTFP isomerization leads to the red shift for DFT methods and to the blue shift in regard to EOM-CCSD and experimental results. The IR absorption spectra are well fitted by B3LYP over the range 500-1600 cm-1 and TPSS0 over 1300-2000 cm-1 for both stereoisomers. Moreover, the root-mean-square errors (RMSEs) of frequencies from experimental data are lower for B3LYP and TPSS0 for both systems. The computed IR absorption band strengths over 500-2000 cm-1 for cis- and over 600-1800 cm-1 for trans-CTFP are consistent with the experiment. The relevant descriptor RFEs of the climate effect were calculated using a narrow band model for a constant vertical profile and then corrected with a lifetime factor for different computational methods. The computed values correlate well with the experimental results for both stereoisomers except M06-2X and TPSS0. It is worth noting that, for both systems, the intense radiative forcing spectra are located at frequencies ranging in 1000-1200 cm-1. The lower forcings of trans-CTFP lying in the atmospheric window region 800-1000 cm-1 are greater than those of cis-CTFP. Therefore, RFE(trans-CTFP) = 1.127 RFE(cis-CTFP).