Effect of alkyl-group flexibility on the melting point of imidazolium-based ionic liquids

Autor(es)

Bernardino, Kalil ^[1] ; Zhang, Yong ^[2] ; Ribeiro, Mauro C. C. ^[1] ; Maginn, Edward J. ^[2]

Afiliação do(s) autor(es)

^[1] Univ Sao Paulo, Dept Quim Fundamental, Inst Quim, Lab Espectroscopia Mol, Av Prof Lineu Prestes 748, BR-05508000 Sao Paulo - Brazil

^[2] Univ Notre Dame, Dept Chem & Biomol Engn, Notre Dame, IN 46556 - USA

• Tipo de documento: Artigo Científico
• Fonte: Journal of Chemical Physics; v. 153, n. 4 JUL 28 2020.
• Citações Web of Science: 0

Resumo

The low melting point of room temperature ionic liquids is usually explained in terms of the presence of bulky, low-symmetry, and flexible ions, with the first two factors related to the lattice energy while an entropic effect is attributed to the latter. By means of molecular dynamics simulations, the melting points of 1-ethyl-3-methyl-imidazolium hexafluorophosphate and 1-decyl-3-methyl-imidazolium hexafluorophosphate were determined, and the effect of the molecular flexibility over the melting point was explicitly computed by restraining the rotation of dihedral angles in both the solid and the liquid phases. The rotational flexibility over the bond between the ring and the alkyl chain affects the relative ordering of the anions around the cations and results in substantial effects over both the enthalpy and the entropy of melting. For the other dihedral angles of the alkyl group, the contributions are predominantly entropic and an alternating behavior was found. The flexibility of some dihedral angles has negligible effects on the melting point, while others can lead to differences in the melting point as large as 20 K. This alternating behavior is rationalized by the different probabilities of conformation defects in the crystal. (AU)

• Processo FAPESP: 16/21070-5 - Espectroscopia vibracional com resolução espacial
• Beneficiário: Mauro Carlos Costa Ribeiro
• Modalidade de apoio: Auxílio à Pesquisa - Temático
• Processo FAPESP: 17/12063-8 - Dinâmica molecular de não-equilíbrio de líquidos iônicos
• Beneficiário: Kalil Bernardino
• Modalidade de apoio: Bolsas no Brasil - Pós-Doutorado
• Processo FAPESP: 19/04785-9 - Estudo por dinâmica molecular do efeito da flexibilidade sobre o ponto de fusão de líquidos iônicos
• Beneficiário: Kalil Bernardino
• Modalidade de apoio: Bolsas no Exterior - Estágio de Pesquisa - Pós-Doutorado