title: Molecular dynamics and a spectroscopic study of sulfur dioxide absorption by an ionic liquid and its mixtures with PEO.
abstract: An investigation comprising experimental techniques (absorption capacity of SO2and vibrational spectroscopy) and molecular simulations (thermodynamics, structure, and dynamics) has been performed for the polymer poly(ethylene oxide) (PEO), the ionic liquid butyltrimethylammonium bis(trifluoromethylsulfonyl)imide ([N4111][Tf2N]) and their mixtures as sulfur dioxide (SO2) absorbing materials. The polymer PEO has higher capacity to absorb SO2than the neat ionic liquid, whereas the mixtures presented intermediary absorption capacities. The band assigned to the symmetric stretching band of SO2at ca. 1140 cm-1, which is considered a spectroscopic probe for the strength of SO2interactions with its neighborhood, shifts to lower wavenumbers as more negative total interaction energy values of SO2were evaluated from the simulations. The solvation free energy of SO2, ΔGsol, correlates linearly with the absorption capacity of SO2. The negative values of ΔGsolare due to negative and positive values of enthalpy and entropy, respectively. In the ionic liquid, SO2weakens the cation-anion interactions, whereas in the mixture with a high content of PEO these interactions are slightly increased. Such effects were correlated with the relative population of cisoid and transoid conformers of Tf2N anions as revealed by Raman spectroscopy. Moreover, the presence of SO2in the systems provokes the increase of diffusion coefficients of the absorbing species in comparison with the systems without the gas. Proper to the slow dynamics of the polymer, the diffusion coefficient of ions and SO2diminishes with the increase of the PEO content.
authors.affiliation: Instituto de Ciências Ambientais, Químicas e Farmacêuticas, Universidade Federal de São Paulo, Rua São Nicolau, 210 Diadema-SP-CEP09913-030, Brazil. ljasiqueira@unifesp.br.
authors.forename: Karina
authors.initials: K
authors.lastname: Hoher
authors.affiliation: Instituto de Ciências Ambientais, Químicas e Farmacêuticas, Universidade Federal de São Paulo, Rua São Nicolau, 210 Diadema-SP-CEP09913-030, Brazil. ljasiqueira@unifesp.br.
authors.forename: Piercarlo F
authors.initials: PF
authors.lastname: Cardoso
authors.affiliation: Instituto de Química, Universidade de São Paulo, São Paulo-SP-CEP 055080-000, Brazil.
authors.forename: Luiz F
authors.initials: LF
authors.lastname: Lepre
authors.affiliation: Instituto de Química, Universidade de São Paulo, São Paulo-SP-CEP 055080-000, Brazil.
authors.forename: Rômulo A
authors.initials: RA
authors.lastname: Ando
authors.affiliation: Instituto de Ciências Ambientais, Químicas e Farmacêuticas, Universidade Federal de São Paulo, Rua São Nicolau, 210 Diadema-SP-CEP09913-030, Brazil. ljasiqueira@unifesp.br.
authors.forename: Leonardo J A
authors.initials: LJ
authors.lastname: Siqueira