Emulating proton transfer reactions in the pseudo-protic ionic liquid 1-methylimidazolium acetate

Jacobi, Richard; Joerg, Florian; Steinhauser, Othmar; Schröder, Christian

doi:10.1039/d2cp00643j

Cited by 10 publications

(26 citation statements)

References 21 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Our simulation still reproduces the equilibrium value of 30% ionic:70% neutral molecules (Jacobi et al, 2022;Joerg and Schröder, 2022) for both s-values as shown in Figure 8.…”

Section: Beforesupporting

confidence: 66%

“…4 to prohibit drifting away from the equilibrium partitioning of the molecules as the total number of proton transfer events, i.e. 5,000, is much lower than in the Markov chain analysis reported by Jacobi et al (2022). Furthermore, due to the distance criterion r max and the mutual orientation of the reacting species in the liquid phase, particular reactions are favored regardless of the value of the reaction probability p ref .…”

Section: Beforementioning

confidence: 92%

“…The simulation period of our polarizable MD simulations is 50 ns. As we stop the production every 10 ps to check for proton exchanges, (Jacobi et al, 2022), a molecule may face 5,000 exchanges at maximum. However, the average number of proton transfers for each molecule is much lower (see in the top panel of Figure 7) and equals roughly 10 to 15 exchanges on average.…”

Section: Beforementioning

confidence: 99%

“…Contrary to common Monte Carlo approaches (Baptista et al, 2002;Mongan et al, 2004) of accepting/denying the proton transfers, we perform the onestep proton hopping with a quantum-mechanically derived probability once a distance criterion between the hopping proton and the acceptor is met. However, our probabilities are determined by a Markov chain model [Jacobi et al (2022)]. In contrast to Dreßler et al, (2020a) and Dreßler et al (2020b) our Markov chain is applied prior to MD simulation to compute reasonable starting probabilities for the various reactions.…”

mentioning

confidence: 99%

“…For imidazoles and acetate, we model the neutral species Im 1 and HOAc and the cation Im 1 H + and anion OAc − , respectively. In principle, it is also possible to model the protonated acetic acid (Ingenmey et al, 2018;Jacobi et al, 2022), which might be necessary for the Grotthus conductivity mechanism, but we restrict ourselves to the simple protonation scheme by Jacobi et al (2022) for the sake of simplicity. The deprotonation of the Im 1 H + or HOAc is modeled by turning the hydrogen (HP) into a dummy atom (DM) which is part of the acetate OAc − and imidazole Im 1 molecule.…”

mentioning

confidence: 99%

See 4 more Smart Citations

Protex—A Python utility for proton exchange in molecular dynamics simulations

Joerg

Wieder²,

Schröder³

2023

Front. Chem.

Self Cite

View full text Add to dashboard Cite

Protex is an open-source program that enables proton exchanges of solvent molecules during molecular dynamics simulations. While conventional molecular dynamics simulations do not allow for bond breaking or formation, protex offers an easy-to-use interface to augment these simulations and define multiple proton sites for (de-)protonation using a single topology approach with two different λ-states. Protex was successfully applied to a protic ionic liquid system, where each molecule is prone to (de-)protonation. Transport properties were calculated and compared to experimental values and simulations without proton exchange.

show abstract

“…Our simulation still reproduces the equilibrium value of 30% ionic:70% neutral molecules (Jacobi et al, 2022;Joerg and Schröder, 2022) for both s-values as shown in Figure 8.…”

Section: Beforesupporting

confidence: 66%

Section: Beforementioning

confidence: 92%

Section: Beforementioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

See 3 more Smart Citations

Protex—A Python utility for proton exchange in molecular dynamics simulations

Joerg

Wieder²,

Schröder³

2023

Front. Chem.

Self Cite

View full text Add to dashboard Cite

show abstract

On the Rich Chemistry of Pseudo‐Protic Ionic Liquid Electrolytes

et al. 2023

View full text Add to dashboard Cite

Mixing weak acids and bases can produce highly complicated binary mixtures, called pseudo‐protic ionic liquids, in which a complex network of effects determines the physicochemical properties that are currently impossible to predict. In this joint computational‐experimental study, we investigated 1‐methylimidazole‐acetic acid mixtures through the whole concentration range. Effects of the varying ionization and excess of either components on the properties, such as density, diffusion coefficients, and overall hydrogen bonding structure were uncovered. A special emphasis was put on understanding the multiple factors that govern the conductivity of the system. In the presence of an excess of acetic acid, the 1‐methylimidazolium acetate ion pairs dissociate more efficiently, resulting in a higher concentration of independently moving, conducting ions. However, the conductivity measurements showed that higher concentrations of acetic acid improve the conductivity beyond this effect, suggesting in addition to standard dilution effects the occurrence of Grotthuss diffusion in high acid‐to‐base ratios. The results here will potentially help designing novel electrolytes and proton conducting systems, which can be exploited in a variety of applications.

show abstract