Short-time collective dynamics of an ionic liquid: A computer simulation study with non-polarizable and polarizable models, and ab initio molecular dynamics

Autor(es)

Paschoal, Vitor Hugo ; Ribeiro, Mauro C. C.

• Tipo de documento: Artigo Científico
• Fonte: Journal of Chemical Physics; v. 161, n. 24, p. 10-pg., 2024-12-28.

Resumo

Molecular dynamics (MD) simulation is used to study the intermolecular dynamics in the THz frequency range of the ionic liquid 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide, [C(2)C(1)im][FSI]. Non-polarizable and polarizable models for classical MD simulation are compared using as quality criteria ab initio molecular dynamics (AIMD) and experimental data from far-infrared (FIR) spectroscopy and previously published data of inelastic x-ray scattering (IXS). According to data from IXS spectroscopy, incorporating polarization in the classical MD simulation has relatively little effect on the dispersion curve (excitation frequency vs wavevector) for longitudinal acoustic modes. When the AIMD simulation is used as a reference, the polarizable model leads the time correlation functions of velocity, mass, and charge currents to relax abnormally quickly. The charge current spectra from the AIMD simulation and the non-polarizable model agree with the experimental FIR spectrum, while the polarizable model gives an excessively broad band. When compared to the non-polarizable model, the polarizable model does improve the calculation of transport coefficients (diffusion coefficient, viscosity, and conductivity); however, it yields overdamped short-time collective dynamics. (AU)

• Processo FAPESP: 22/11983-4 - Espectroscopias com intensificação de sinal: nanomateriais, teoria e simulação computacional
• Beneficiário: Mauro Carlos Costa Ribeiro
• Modalidade de apoio: Auxílio à Pesquisa - Temático
• Processo FAPESP: 19/00207-0 - Teoria do funcional da densidade aplicada a dinâmica vibracional de cristais de sistemas iônicos.
• Beneficiário: Vitor Hugo Paschoal
• Modalidade de apoio: Bolsas no Brasil - Pós-Doutorado