scispace - formally typeset
Open AccessJournal ArticleDOI

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

Reads0
Chats0
TLDR
By means of molecular dynamics simulations, the melting points of 1-ethyl-3-methyl-imidazolium hexafluorophosphate and 1-decyl- 3- methyl-IMidazlium hexAFluorophile 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.
Abstract
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.

read more

Citations
More filters

Fast parallel algorithms for short-range molecular dynamics

TL;DR: Comparing the results to the fastest reported vectorized Cray Y-MP and C90 algorithm shows that the current generation of parallel machines is competitive with conventional vector supercomputers even for small problems.
Journal ArticleDOI

Targeted modifications in ionic liquids – from understanding to design

TL;DR: In this paper, targeted modifications are discussed as a powerful tool to provide understanding and to enable design of ionic liquids, where a targeted modification is a deliberate change in the structure of an ionic liquid, such as chemical changes in an experiment as well as changes to the parameterisation in a computer simulation.
Journal ArticleDOI

A review on machine learning algorithms for the ionic liquid chemical space

TL;DR: In this article, the use of machine learning algorithms as property prediction tools for ionic liquids (either as standalone methods or in conjunction with molecular dynamics simulations), presents common problems of training datasets and proposes ways that could lead to more accurate and efficient models.
Journal ArticleDOI

Role of density and electrostatic interactions in the viscosity and non-newtonian behavior of ionic liquids - a molecular dynamics study.

TL;DR: In this paper , the effect of ionic interactions and the increase of liquid density contribute to the high viscosity and so far no experimental or computational work enabled a clear quantification of those effects.
Journal ArticleDOI

Does Explicit Polarizability Improve Simulations of Phase Behavior of Ionic Liquids

TL;DR: In this article, the fusion enthalpy of 20 aprotic ionic liquids is calculated using a nonpolarizable all-atom optimized potentials for liquid simulations (OPLS) force-field model.
References
More filters
Journal ArticleDOI

VMD: Visual molecular dynamics

TL;DR: VMD is a molecular graphics program designed for the display and analysis of molecular assemblies, in particular biopolymers such as proteins and nucleic acids, which can simultaneously display any number of structures using a wide variety of rendering styles and coloring methods.
Journal ArticleDOI

Fast parallel algorithms for short-range molecular dynamics

TL;DR: In this article, three parallel algorithms for classical molecular dynamics are presented, which can be implemented on any distributed-memory parallel machine which allows for message-passing of data between independently executing processors.

Fast parallel algorithms for short-range molecular dynamics

TL;DR: Comparing the results to the fastest reported vectorized Cray Y-MP and C90 algorithm shows that the current generation of parallel machines is competitive with conventional vector supercomputers even for small problems.
Journal ArticleDOI

Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy

TL;DR: A large set of more than 300 molecules representing all elements-except lanthanides-in their common oxidation states was used to assess the quality of the bases all across the periodic table, and recommendations are given which type of basis set is used best for a certain level of theory and a desired quality of results.
Journal ArticleDOI

A unified formulation of the constant temperature molecular dynamics methods

TL;DR: In this article, the authors compared the canonical distribution in both momentum and coordinate space with three recently proposed constant temperature molecular dynamics methods by: (i) Nose (Mol. Phys., to be published); (ii) Hoover et al. [Phys. Rev. Lett. 77, 63 (1983); and (iii) Haile and Gupta [J. Chem. Phys. 79, 3067 (1983).
Related Papers (5)