Infrared absorption spectra of linear (L2–L5) and cyclic (D3–D6) permethylsiloxanes. (November 2017)

• Record Type: Journal Article
• Authors: Bernard, François; Papanastasiou, Dimitrios K.; Papadimitriou, Vassileios C.; Burkholder, James B.
• Is Part Of: Journal of quantitative spectroscopy & radiative transfer. Volume 202(2017)
• Page Start: 247
• Page End: 254
• Publication Date: 2017-11
• Subjects: Permethylsiloxane -- Infrared spectra -- Theoretical calculations -- Radiative efficiency -- Global warming potential; Spectrum analysis -- Periodicals; Radiation -- Periodicals; Analyse spectrale -- Périodiques; Rayonnement -- Périodiques; Radiation; Spectrum analysis; Periodicals; 543.0858
• DOI: 10.1016/j.jqsrt.2017.08.006
• Languages: English
• ISSNs: 0022-4073

Abstract

Highlights: Quantitative infrared absorption spectra of several linear and cyclic permethylsiloxanes are reported. Infrared absorption spectra calculated using DFT methods are in good agreement with the measured spectra. Permethylsiloxanes are shown to be potent greenhouse gases. Abstract: Absolute infrared absorption spectra of the linear (hexamethyldisiloxane ((CH3 )3 SiOSi(CH3 )3, L2 ), octamethyltrisiloxane ([(CH3 )3 SiO]2 Si(CH3 )2, L3 ), decamethyltetrasiloxane ([(CH3 )3 SiO]2 (Si(CH3 )2 OSi(CH3 )2 ), L4 ), dodecamethylpentasiloxane ([(CH3 )3 SiO]2 (Si(CH3 )2 OSi(CH3 )2 OSi(CH3 )2 ), L5 ), and cyclic hexamethylcyclotrisiloxane ([Si(CH3 )2 O]3, D3 ), octamethylcyclotetrasiloxane ([Si(CH3 )2 O]4, D4 ), decamethylcyclopentasiloxane ([Si(CH3 )2 O]5, D5 ), and dodecamethylcyclohexasiloxane ([Si(CH3 )2 O]6, D6 )) permethylsiloxanes were measured over the 600–4000 cm −1 spectral region at 294 K using Fourier transform infrared (FTIR) spectroscopy at 1 cm −1 resolution. Measurements were performed using manometrically prepared dilute permethylsiloxane mixtures in a He bath gas and infusion of the pure compound into a calibrated gas flow. Theoretical calculations at the B97-1/6-311++G(2df, 2p) level of theory were performed and optimized permethylsiloxane geometries and vibrational band positions and strengths are reported. The theoretically calculated infrared spectra are compared with the experimental spectra and found to be in good agreement. The radiative efficiencies (RE) of the permethylsiloxanes were calculated and found to be extremely large in comparison with other atmospheric greenhouse gases, with values ranging from 0.55 to 2.02 W m −2 ppb −1 for a uniform atmospheric distribution, i.e., well-mixed scenario.