Autor(es)

Bernardino, Kalil ^[1] ; Lima, Thamires A. ^[1] ; Ribeiro, Mauro C. C. ^[1]

Afiliação do(s) autor(es)

^[1] Univ Sao Paulo, Lab Espect Mol, Dept Quim Fundamental, Inst Quim, BR-05508000 Sao Paulo, SP - Brazil

• Tipo de documento: Artigo Científico
• Fonte: Journal of Physical Chemistry B; v. 123, n. 44, p. 9418-9427, NOV 7 2019.
• Citações Web of Science: 0

Resumo

Several calorimetric measurements have shown that 1-ethyl-3-methylimidazolium dicyanamide, {[}C(2)C(1)im]{[}N(CN)(2)], is a glass-forming liquid, even though it is a low-viscous liquid at room temperature. Here, we found slow crystallization during cooling of {[}C(2)C(1)im]{[}N(CN)(2)] along Raman spectroscopy measurements. The low-frequency range of the Raman spectrum shows that the same crystalline phase is obtained at 210 K either by cooling or by reheating the glass (cold-crystallization). Another crystalline phase is formed at ca. 260 K just prior the melting at 270 K. X-ray diffraction and calorimetric measurements confirm that there are two crystalline phases of {[}C(2)C(1)im]{[}N(CN)(2)]. The Raman spectra indicate that polymorphism is related to {[}C(2)C(1)im](+) with the ethyl chain on the plane of the imidazolium ring (the low-temperature crystal) or nonplanar (the high-temperature crystal). The structural reason for the glass-forming ability of {[}C(2)C(1)im]{[}N(CN)(2)], despite the relatively simple molecular structures of the ions, was pursued by quantum chemistry calculations and molecular dynamics (MD) simulations. Density functional theory calculations were performed for ionic pairs in order to draw free-energy surfaces of the anion around the cation. The MD simulations using a polarizable model provided maps of occurrence of anions around cations. Both the quantum and classical calculations suggest that the delocalization of preferred positions of the anion around the cation, which adopts different conformations of the ethyl chain, is on the origin of the crystallization being hampered during cooling and the resulting glass-forming ability of {[}C(2)C(1)im]{[}N(CN)(2)]. (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: 14/15049-8 - Estudo por espectroscopia Raman da transição vítrea de líquidos iônicos em alta pressão.
• Beneficiário: Thamires Andrade Lima
• 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