2023
DOI: 10.1021/acs.jpcc.3c03484
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Correlation of Dielectric Properties with Structure and H-Bonding for Liquids

Elliot L. Bennett,
Ilkan Calisir,
Xiantao Yang
et al.

Abstract: A study focused on the correlation among dielectric properties, molecular structure, and H-bonding is presented using liquid formamides with increasing carbon chain lengths as a model series. 1 H NMR is used to determine the extent of H-bonding via Abraham solute hydrogen bond acidity parameter, A. The results show a clear quantitative correlation, with higher A linked with increased relaxation times (τ) and a drop in the static dielectric constants (ε s ), with differences between the 1 and 2°amides observed.… Show more

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Cited by 11 publications
(3 citation statements)
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“…From the remaining 40 ns, 400 non‐equilibrium transitions of 500 ps each were generated and work values from the forward and backward transitions were collected using thermodynamic integration. These values were then used to estimate the corresponding free energy difference with Bennett's acceptance ratio 61 as a maximum likelihood estimator relying on the Crooks fluctuation theorem 62 . Bootstrapping was used to estimate the uncertainties of the free energy estimates, 53,63 and these were propagated when calculating ΔΔG values.…”
Section: Methodsmentioning
confidence: 99%
“…From the remaining 40 ns, 400 non‐equilibrium transitions of 500 ps each were generated and work values from the forward and backward transitions were collected using thermodynamic integration. These values were then used to estimate the corresponding free energy difference with Bennett's acceptance ratio 61 as a maximum likelihood estimator relying on the Crooks fluctuation theorem 62 . Bootstrapping was used to estimate the uncertainties of the free energy estimates, 53,63 and these were propagated when calculating ΔΔG values.…”
Section: Methodsmentioning
confidence: 99%
“…For solvation free energy calculation, a single pair of Li salt (i.e., LiFSI, LiBF 4 , and LiOTf) was placed with 200 solvent molecules (i.e., DME or SN). [ 52 ] Initially, all systems were subjected to NPT MD simulation to equilibrate the systems for 1 ns. Subsequently, the solvation free energies were calculated using acceptance ratio method under the NVT ensemble at room temperature.…”
Section: Methodsmentioning
confidence: 99%
“…Note that the origin of the high e r in F is the same as that in NMF. 420 Although Jousset et al did not report the residual concentration in their NMF, the residual salt of commercial NMF grades has been reported to be as high as 0.02 M. 421,422 Therefore, assuming f = 1 and c s = 0.02 M, we estimated c* in salt-free NMF, which yielded c* C 6 Â 10 À3 M. As seen as a filled square and an inverted triangle in Fig. 12, both scenarios appear insufficient to fully account for the drastic change of c* in magnitude.…”
Section: Conformation In Salt-free Solution At Infinite Dilutionmentioning
confidence: 99%